10 1021@acs Chemrev 6b00076

Review
pubs.acs.org/CR
Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic

Compounds: Synthetic Routes, Properties, and Applications
Marcin Stpien,* Elzb ieta Gonka, Marika Z ya, and Natasza Sprutta
Wydzia Chemii, Uniwersytet Wrocawski, ul. F. Joliot-Curie 14, 50-383 Wrocaw, Poland
ABSTRACT: Two-dimensionally extended, polycyclic heteroaromatic molecules
(heterocyclic nanographenes) are a highly versatile class of organic materials, applicable
as functional chromophores and organic semiconductors. In this Review, we discuss the
rich chemistry of large heteroaromatics, focusing on their synthesis, electronic properties,
and applications in materials science. This Review summarizes the historical development
and current state of the art in this rapidly expanding eld of research, which has become
one of the key exploration areas of modern heterocyclic chemistry.
CONTENTS
1. Introduction
1.1. Background
1.2. Scope
1.2.1. Fusion Patterns
1.2.2. Molecular Size and Structure
1.2.3. Literature Scope
1.3. Classication and Nomenclature
1.4. Synthetic Strategies
1.4.1. Dehydrogenative (Oxidative) Annulations
1.4.2. Other Direct Annulations
1.4.3. Bay-Region Cyclizations
1.4.4. Electrophilic Condensations
2. Coronenoids
2.1. Edge-Doped Aza- and Oxacoronenes
2.1.1. Diazacoronenes
2.1.2. Dioxacoronenes
2.1.3. Triazacoronenes
2.1.4. Tetraazacoronenes
2.2. Pyrrole-Fused Azacoronenes
2.3. B- and BN-Doped Coronenes
2.3.1. Diboracoronenes
2.3.2. BN-Embedded Systems
2.4. peri-Condensed Coronenes
2.5. ortho-Condensed Coronenoids
2.5.1. Coronenoids Fused to Azaheterocycles
2.5.2. Thieno-Fused Coronenoids
3. Perylenoids
3.1. Heteraperylenoids
3.1.1. Monoheteraperylenoids
3.1.2. Diheteraperylenoids
3.1.3. Tetraheteraperylenes
XXXX American Chemical Society
3.2. [ghi]Heteroannulated Perylenoids: 5-Membered Rings

3.4. [cd]Heteroannulated Perylenoids
3.5. ortho-Heteroannulated Perylenoids
4. Pyrenoids
4.1. Triangulenes
4.2. Azapyrenoids
4.2.1. Boron-Containing Azapyrenoids
4.3. Oxa- and Thiapyrenoids
4.4. [cd]-Heterofused Pyrenoids
4.5. [a]-Heterofused Pyrenoids
4.5.1. Direct Pyrrole Fusion
4.5.2. Other N-Containing Systems
4.5.3. Other Five-Membered Rings
4.6. Pyrazacenes
4.6.1. Pyrazine-Fused Systems
4.7. Other [e]Fused Pyrenoids
4.7.1. Pyrrole- and Indole-Containing Systems
4.7.2. Imidazole-Containing Systems
4.7.3. Other Nitrogen-Containing Systems
4.7.4. Oxygen-Containing Systems
4.7.5. Sulfur-Containing Systems
5. Phenalenoids
5.1. Monoheteraphenalenes
5.1.1. Heterahelicenes
5.1.2. 9a-Azaphenalene Ylides
5.1.3. Ceramidonines
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B
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Special Issue: Expanded, Contracted, and Isomeric Porphyrins

Received: January 30, 2016
DOI: 10.1021/acs.chemrev.6b00076
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
5.1.4. Dibenzo[c,mn]acridin-8-ones
5.1.5. Monooxa- and Monothiaphenalenoids
5.1.6. Miscellaneous Azaphenalenoids
5.2. Diheteraphenalenes
5.2.1. Pyridoacridines
5.2.2. Other 1,6-Diheteraphenalenoids
5.2.3. 1,4-Diheteraphenalenoids
5.2.4. 1,3a-Diheteraphenalenoids
5.3. Tri- and Tetraheteraphenalenes
5.3.1. Tricycloquinazolines and Related Systems
5.4. Phenalenoids with Nonbenzenoid peri-Fusion
5.4.1. Cyclopenta[cd]phenalenes
5.4.2. Cyclohepta[cd]phenalenes
6. Nonbenzenoid Fusion
6.1. Circulenoids and Related Systems
6.1.1. Heterofused Circulenes
6.1.2. [5]Heteracirculenoids
6.1.3. [6]Heteracirculenoids
6.1.4. [7]Heteracirculenes
6.1.5. [8]Heteracirculenes
6.1.6. Larger Systems
6.2. Fused Acenaphthylene Derivatives
6.2.1. Hetero[a]fused Acenaphthylenes
6.2.2. Hetero[e]fused Acenaphthylenes
6.2.3. Hetero[d]fused Acenaphthylenes
6.2.4. Carbazole-Based and Related Systems
6.2.5. Carbonyl-Free Azauoranthenes
6.2.6. Miscellaneous Azaacenaphthylenes and
Azauoranthenes
6.2.7. Pyracylene-Based Systems
6.2.8. Extended Thiaacenaphthylenes
6.2.9. Fused Oxaacenaphthylenes
6.3. Cyclopenta[cd]indene Systems
6.3.1. Fused Pyrrolo[3,2,1-hi]indoles
6.3.2. Fused Pyrrolo[2,1,5-cd]indolizines
6.4. peri-Fused Seven-Membered Rings
6.4.1. peri-Fused Cycloheptatrienes
6.4.2. Fused Azepines and Diazepines
6.4.3. Oxa- and Thia- 7-Membered Rings
7. Macrocyclic Systems
7.1. [b]-Fused (-Fused) Porphyrinoids
7.2. Benzo[cd]-Fused Porphyrinoids
7.2.1. Benzo[cd]-Fusion via meso-Substituent
Coupling
7.2.2. Other Benzannulations
7.2.3. Pyrido[cd]fused Systems
7.2.4. Pyrano- and Thiopyrano[cd]fused Systems
7.2.5. Benzo-Fused Porphyrin Oligomers
7.2.6. Oxonaphtho-Fused Porphyrins and Benzooxochlorins
7.2.7. Indole- and Carbazole-Based Porphyrinoids
7.3. Naphtho[2,1,8,7-cdef ]-Fused Porphyrinoids
7.3.1. Arene-Fused Systems
7.3.2. Porphyrin Tapes
7.4. [cd]-Fused Porphyrinoids with 5- and 7Membered Rings
7.4.1. Dehydropurpurins
7.4.2. Indeno[1,2,3-cd]porphyrins
7.4.3. Other Cyclopenta-Fused Systems
Review
7.4.4. Fused 7-Membered Rings

7.5. Porphyrinoids with Polycyclic Subunits
7.5.1. Porphyrinoids with Benzannulated Bipyrrole Units
7.5.2. Cyclooctatetraene-Fused Systems
7.5.3. Thiophene-Fused Systems
7.5.4. Systems with Acene and Heteroacene
Subunits
7.5.5. Systems with Macrocyclic Subunits
7.6. Internally Fused Porphyrinoids
7.6.1. Regular Porphyrins
7.6.2. N-Confused Porphyrins
7.6.3. Pentaphyrins
7.6.4. Hexaphyrins
7.6.5. Heptaphyrins
7.6.6. Other Porphyrinoids
7.7. peri-Fused Cyclophanes
7.7.1. peri-Fused Pyridine Cyclophanes
7.7.2. peri-Fused Pyrrole Cyclophanes
7.7.3. Sulfur-Containing peri-Fused Cyclophanes
7.7.4. Oxygen-Containing Cyclophanes
7.7.5. Heteroatom-Bridged Cyclophanes
8. Conclusions and Outlook
Author Information
Corresponding Author
Notes
Biographies
Acknowledgments
Abbreviations
References
CR
CR
CT
CT
CT
CV
CX
CX
CY
CY
DA
DA
DC
DC
DC
DD
DD
DE
DG
DH
DJ
DL
DL
DO
DO
DO
DQ
DQ
DS
DS
DT
DU
DU
DU
DU
DU
DW
DY
DZ
EB
ED
FO
FP
FP
FS
FS
FT
FU
FV
FV
FW
FY
GA
GA
GB
GB
GB
GE
GI
GJ
GJ
GL
GL
GL
GL
GL
GM
GM
GN
1. INTRODUCTION
1.1. Background
The chemistry of heteroaromatic compounds is a vast

discipline, spanning nearly two centuries of research. The
focus of heterocyclic chemistry has evolved over time, to
encompass a multitude of topics in synthetic and physical
organic chemistry, natural product research, molecular biology,
and materials science. The interest in polycyclic heteroaromatic
molecules (PHAs), which are the subject of the present review,
can be traced back to the initial investigations of natural and
synthetic dyes (Chart 1; note the dierence between PHA and
PAH, the latter denoting a polycyclic aromatic hydrocarbon).1,2
The elucidation of the structure of avanthrone, accomplished
by Roland Scholl in 1907,3 was among the most prominent
early achievements, because of avanthrones unique eight-ring
structure and its industrial relevance. The initial development of
the eld was often hampered by the lack of appropriate
analytical methods: it had taken decades of research until the
structures of xylindein, tricycloquinazoline, and tetrabenzotetraoxa[8]circulene were unequivocally determined.
In the following years, the eld gradually expanded from
dyestu research, to include other areas of theoretical and
practical importance. The interest in the mechanism of PAH
carcinogenicity4 became one of the major research motivations
in the 1950s. In the following two decades, a remarkable
number of new PHA structures were reported, notably by the
groups of Partridge and Buu-Ho. New work on large
polyheterocycles was subsequently inspired by the demands
of supramolecular chemistry, by the growing interest in
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However, current production methods10,11 lead to random

incorporation of the dopant, and ne structural details
regarding heteroatom doping are often unavailable. There are
also intrinsic limits regarding the level and pattern of doping
achievable using high-temperature methods.12 At the same
time, incorporation of heteroatoms in graphene can induce or
enhance desirable properties, such as electrochemical activity,
charge polarization, bandgap opening, and n- or p-type
semiconductor characteristics.1315 This principle is applicable
to other carbon-rich materials, and heteroatom doping is
employed as a means of bandgap tuning in -conjugated
polymers,16 and graphene nanoribbons,17 and for creating
small-molecule n-type semiconductors.18
In this context, extensively fused heterocyclic systems are
seen as doped nanographenes, combining structural uniformity
with tunable electronic structure. Two-dimensional extension
of the -conjugated framework, which is the dening feature of
nanographene structures, can provide faster reduction of the
HOMOLUMO gap than observed in structurally similar
linear (i.e., 1D-extended) molecules.19 By modifying the
topology and heteroatom content of the -conjugated system,
it is possible to control key features of the electronic structure,
including the band gap, optical absorption spectra, photoluminescence, and redox behavior. Because these parameters
can be tuned very exibly, many families of PHAs are attractive
objects of photophysical investigations, and have been explored
as NIR-active dyes,20,21 two-photon absorbers,22 and uorescence sensors. The presence of heteroatoms facilitates the
design of stable -aromatic cations,23 high-spin organic
molecules,24 and ligands for transition metals. Depending on
the number and placement of heteroatom donors, PHAs can
oer monodentate, chelating, or macrocyclic coordination,
leading to the formation of mono- and polynuclear complexes,
which have been investigated for their photophysical properties,
biological activity, and supramolecular behavior.
Since the early days of PHA chemistry, nitrogen has been the
primary dopant element, a choice dictated by the availability
of synthetic methods and the stability of the N-containing
systems. Considerable eort is now being directed toward the
development of large heteroaromatics containing boron,25
phosphorus,26,27 or chalcogens.28 This expanding portfolio of
usable heteroatoms provides an additional variable in the design
of functional PHA molecules.
Because of their anisotropic molecular shapes, structural
rigidity, and extended -surfaces, polycyclic heteroaromatics are
of particular interest as self-assembling materials. Importantly,
the presence of heteroatoms in PHAs introduces intrinsic
dipole moments and edge functionalities, which can be used as
additional means of controlling the molecular organization. In
the following sections, we will present numerous examples of
self-assembling PHAs, displaying a great variety of organization
types, including crystals, liquid crystals, porous materials,
nanobers, and gels. In addition to bulk self-assembly, PHAs
often provide ecient organization in solution and as
monolayers. PHAs are also useful as building blocks for
covalent assembly, and have been employed for constructing
conjugated polymers, including donoracceptor and laddertype materials, graphene nanoribbons, and nite-length
oligomers.
PHA molecules thus oer a unique combination of tunable
electronic structure with excellent self-assembling properties,
which is highly desirable in materials science. By judicious
choice of ring fusion, heteroatom doping, and substitution,
Chart 1. Early Examples of Two-Dimensionally Fused

Heterocycles
porphyrin analogues, and by advances in natural product

chemistry, in particular by the discovery of pyridoacridine
alkaloids.
Figure 1 provides a pictorial summary of the most active
areas of modern PHA research, which are discussed in the
following sections of this Review. These developments have
been made possible by considerable improvements in synthetic
methodology, which largely eliminated the harsh reaction
conditions prevalent in the early work on PHAs and enabled
preparation of highly functionalized, solution-processable
derivatives. Transition metal-catalyzed coupling reactions are
arguably the most important recent addition to the synthetic
toolbox, and have been extensively used in modern PHA
chemistry. The tasks that can be accomplished with catalyzed
couplings include not only annulation reactions and installation
of functional groups, but also the elaboration of oligoaryl
precursors, which can then be cyclized to PHA targets using, for
example, oxidative coupling reactions.5 Advances in macrocyclic
chemistry, most notably in the synthesis of porphyrin
analogues, have also been instrumental in shaping the eld of
PHA chemistry, providing access to structures of exceptional
complexity.
At the turn of the 21st century, the research on large
polycyclic heteroaromatics gained new impetus with the
discovery of graphene and with the prospect of its application
in molecular electronics. The use of graphene as a semiconductor for postsilicon electronics is limited by its problematic production and handling, because currently available
technology does not provide straightforward access to
structurally uniform material. Furthermore, the requirement
of a nonzero bandgap makes large-area graphene unsuitable in
some key applications, such as eld-eect transistors.6 The
bandgap can be opened by lateral or two-dimensional
connement in graphene nanoribbons (GNRs) and nanographenes (graphene quantum dots, GQDs), respectively.
Bottom-up synthetic approaches can provide such materials
with atomic-level uniformity, as has been demonstrated by
numerous syntheses of extended PAHs using solution
chemistry.7,8
In molecular electronics, heteroatom doping of graphene is
of high importance, as it changes the electronic structure of the
material, opening new possibilities for device applications.9
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Figure 1. Research directions in modern PHA chemistry.
Figure 2. Citation timeline of this Review. The scope of the literature search is dened in the text.
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The above restriction means that purely ortho- or macrofused systems, even of large sizes, will be excluded from this
Review. This class of structures includes linearly and angularly
fused oligoacene analogues, as well as a number of branched
ortho-fused systems, the latter often having a distinct twodimensional look. Several important classes of organic materials
belong here, including linear heteroacenes,18,30,31 heterahelicenes,32 thiophene-based systems,33 indolocarbazoles,34 BNdoped aromatics,25 phosphole-based systems,26,27 and several
types of macrocyclic molecules.
1.2.2. Molecular Size and Structure. This Review is
further limited to systems that contain a contiguously conjugated framework with at least 20 sp2-hybridized atoms.
This arbitrary limit, which typically corresponds to systems
containing at least ve or six fused rings, was selected through
preliminary literature searches, to provide a reasonable number
of references. We believe that through this choice, the focus of
this Review is improved, by highlighting the chemistry that has
the highest potential of creating particularly large structures.
Nevertheless, smaller PHAs are occasionally included, whenever they provide a relevant context for discussion. Some
aspects of the chemistry of smaller peri-annulated heterocycles
were reviewed by Mezheritskii35 and by Aksenov et al.36 The
majority of nanographene molecules have approximately planar
geometries; however, even highly distorted -systems will be
included in this Review, provided that the distortion does not
interrupt the continuity of -conjugation.
As a general rule, any ring containing a tetravalent center will
not normally be regarded as part of the fused system. Rings
containing hypervalent heteroatoms and metallacycles are also
excluded. Otherwise, any array of planarly hybridized carbons
and heteroatoms will be considered contiguously -conjugated,
regardless of the formal valence structure. It will thus be
assumed that the conjugation is not interrupted by exocyclic
double bonds emanating from the fused framework (such as
vinylidene or carbonyl groups), carbocationic or radical centers,
etc. Oxygen and sulfur atoms, both di- and trivalent, will
normally be considered part of the -conjugated structure.
Fused systems containing triple bonds, usually embedded in
macrocyclic rings, are discussed when their structures are
conformationally rigid and approximately planar. It should be
noted that a number of exible ultralarge acetylene macrocycles, such as those developed by the groups of Anderson37
and Wurthner,38 which formally meet topological criteria for
inclusion, are not discussed here.
As an exception to the above rules, the presence of a cyclic
imide and anhydride moiety in a molecule will typically not be
considered sucient for inclusion in this Review. This decision
serves to eliminate a large number of structurally similar
molecules, mostly N-substituted derivatives of perylene- and
naphthalenediimides (PDIs and NDIs, respectively), and
related rylene derivatives. PDIs and NDIs will however be
discussed whenever they contain another PHA system of
interest. Various aspects of rylene chemistry have been
reviewed by the groups of Langhals,39 Li,40 Marder,41
Mullen,4245 Wang,46 Wudl,47 and Wurthner.4851 Lactone
rings are typically omitted as well, whereas conjugated lactam
substructures, such as 2-pyridone rings, are normally retained
because of their possible tautomerism.
1.2.3. Literature Scope. This Review attempts to cover the
relevant work published since the late 19th century to the end
of 2015. Even with the above restrictions, this Review spans a
broad range of topics, which were partly reviewed by other
PHAs can be tailored into both p- and n-type semiconductors

and have found extensive use in organic eld-eect transistors
and organic light emitting diodes. Photovoltaic applications of
PHAs encompass both bulk-heterojunction (BHJ) and dyesensitized (DS) solar cells, with many examples presented
below.
Driven by such a diversity of stimuli, the area of PHA
chemistry has become very heterogeneous. While certain
subelds of this research have been reviewed, as discussed
below, it seems that no unied view of the eld has been
oered so far. This Review aims to ll this gap by exploring the
topological diversity of existing PHA molecules and bringing
together pieces of research that have been developed in
dierent research contexts.
1.2. Scope
This Review is focused on heteroaromatic systems in which the

fused ring framework forms a distinct two-dimensional
structure. In hydrocarbon chemistry, such molecules are
typically called nanographenes, and the term is conveniently
applied also to heterocyclic and nonbenzenoid analogues.
While the above denition seems intuitively clear, it has to be
rened in terms of molecular size and fusion patterns, to keep
the review within a manageable length. Our primary purpose is
to document the explosive growth of the eld, which has
occurred during the last 15 years (Figure 2), while also
providing a concise account of earlier developments.
1.2.1. Fusion Patterns. First, we restrict the scope to
systems that are ortho- and peri-fused, according to the
IUPAC denition29 (Chart 2). Such systems are characterized
Chart 2. Examples of ortho-, peri-, and macro-Fusion
by the presence of three-ring junctions (red dots, Chart 2),

which we will call peri-fusion points in the following
discussion. In common use, the IUPAC term ortho- and
peri-fused is often abbreviated to peri-fused or periannulated, and we will also follow this convention here. A
fusion situation not covered by the ortho/peri nomenclature
involves pairs of rings that share more than one edge (i.e., more
than two atoms). As this type of fusion typically occurs in
macrocyclic systems (e.g., in porphyrin), we will label it macrofusion for convenience. A range of highly interesting molecules
exist in which a peri-fusion point results from a combination of
ortho- and macro-fusion, as in the cyclopenta-fused porphyrin
analogue, known as dehydropurpurin (cf., section 7.4). The
scope of this work will be accordingly expanded to include such
ortho-, macro-, and peri-fused systems.
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Chart 3. Examples of peri-Condensed Frameworks Discussed in This Reviewa
Heteroatom placement and double bonds are not indicated.
authors. Related review articles are cited at the beginning of

each major section. Patent literature is generally excluded,
unless the claims are of historical importance or have been

veried in subsequent nonpatent work. Older reports with
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Scheme 1. Typical Synthethic Transformations Based on ortho- and peri-Annulations (Red Bonds) and Oligomer Formation
(Purple Bonds)a
Popular types of aromatic oligomers are shown in box B. Examples of linking multiple fused systems via annulation chemistry are shown in box C.
produced peri-fusion points or formed the heterocyclic

substructure of interest. Nonsynthetic aspects of PHA
chemistry, including spectroscopy, electrochemistry, device
fabrication, theoretical investigations, etc., are presented in
detail for the most recent advances in the eld. Isolation and
structural determination of natural products is beyond the
scope of this work.
insucient analytical data and no follow-up work are usually

cited without an in-depth discussion.
This Review is principally focused on synthetic methodology,
with a particular emphasis on bottom-up, atomically precise
syntheses of monodisperse systems. Nevertheless, relevant
polymeric structures, such as heteroaromatic nanoribbons, are
presented in the context of related nanographene chemistry.
Heterofullerene derivatives52 and heterocycle-modied fullerenes53 are considered structurally and synthetically distinct
from PHAs and will not be covered here.
The majority of reactions discussed herein pertain to the
realm of solution chemistry, with just a few examples of gasphase syntheses of some highly strained molecules. In addition
to conventional bulk synthesis, we present pertinent advances
in the on-surface preparation of heteroaromatic systems. With
the submolecular resolution of the current AFM methodology,
such reactions can be followed on surface in remarkable detail.
Synthetic routes leading to PHA targets typically involve
multistep reaction sequences. To avoid presenting routine
synthetic work, we usually limit our discussion to the key
transformations of the fused framework, particularly those that
1.3. Classication and Nomenclature
Polycyclic heteroaromatic molecules presented in this Review

display considerable structural diversity in terms of such
features as the number and connectivity of constituent rings,
heteroatom pattern, and peripheral substitution. The classication used in this work orders the material according to the
decreasing extent of benzenoid (graphene-like) ring fusion
(Chart 3). The proposed classication has no chemical
signicance and was chosen to present related contributions
in a coherent fashion. In the interest of clarity, we sometimes
depart from the main classication scheme, as discussed below.
Nevertheless, some splitting of associated work (sometimes
within a single paper) could not be avoided. We compensate
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Scheme 2. Selected peri-Annulation Methods
pyrrole instead of isoindole), and are usually motivated by the

research context.
for this occasional inconvenience by providing relevant crossreferences.

We begin with discussing coronenoids, molecules that
contain a coronene substructure (section 2) that is either
heteroatom-doped itself or fused to a heterocyclic subunit.
Some of the largest heteroaromatic nanographenes are
discussed here, which typically have a sheet-like rather than
ribbon shape. By selecting systems with progressively smaller
benzenoid substructures, the remaining material is further
divided into perylenoids (section 3), pyrenoids (section 4), and
phenalenoids (section 5). All of these systems possess at least
one benzenoid peri-fusion point, that is, a junction common
to three six-membered rings. It should be noted that the
coronene and perylene motifs satisfy the size criterion without
fusion of additional rings, whereas pyrene substructures need to
be expanded with at least one additional cycle. Similarly, the
section on phenalenoids covers systems containing at least 5
fused rings.
The remaining systems, which do not possess a phenalene
substructure, are classied as nonbenzenoid in this Review
(section 6). Here, the ortho- and peri-fused substructures
typically contain at least one ve- or seven-membered ring,
although a number of systems containing larger cycles are also
classied in this section (e.g., circulenoids). This Review
concludes with section 7, which covers macrocyclic systems
containing ortho-, macro-, and peri-fused motifs. For convenience, these systems are further divided into porphyrinoids and
cyclophanes, depending on the choice of the original authors.
The nomenclature used in the original work is usually
retained even when it does not strictly follow IUPAC rules.
Departures from IUPAC naming recommendations typically
involve a nonstandard choice of the parent component (e.g.,
1.4. Synthetic Strategies
As with any class of cyclic molecules, the major challenge in

PHA chemistry is posed by the need to design eective
annulation strategies. Because of the structural diversity of PHA
systems and the complexity of existing ring fusion patterns,
several distinct synthetic approaches have emerged, which are
applicable, often in a rather limited fashion, to particular classes
of compounds. The basic ring forming operations can be
broadly classied as ortho- and peri-annulations (Scheme 1, box
A). ortho-Annulations typically provide lateral or peripheral
extensions of the existing fused framework. One-step reactions
leading directly to a -conjugated ring are preferred, although in
rare cases aliphatic rings are constructed rst and subsequently
aromatized (e.g., 36.16).
Alternatively, ortho-annulations can be used to establish a
fused connection between two ring systems, thereby rapidly
increasing structural complexity (Scheme 1, box C). The
condensation of ortho-diamines with 1,2-diones is particularly
useful for the latter purpose, yielding pyrazine (quinoxaline)
connections (cf., Schemes 22, 28, and sections 4.6 and 6.2).
Similar fused connections can be created by condensing
aromatic diamines with cyclic anhydrides, to produce
imidazole- or pyrimidine-containing junctions (cf., Schemes
59, 91, 110), or by other specic annulations leading to, for
example, pyrrole (152.4) or thiophene rings (144.17). orthoAnnulations involving more than two polycyclic molecules can
be used to create branching points in the fused structures;
relevant examples discussed in the following sections include
Heck-type trimerizations leading to benzene rings (155.2,
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that is, it involves the formation of a new ring via intramolecular

coupling of two aromatic subunits. Dehydrogenative annulations were originally developed in the early phase of aromatic
chemistry (notably through the work of Scholl and coworkers), but they remain of high interest because of their
utility in the synthesis of large fused systems such as HBC
derivatives (section 2) or peripherally fused porphyrinoids
(sections 7.2 and 7.3). The chemistry usually involves an
oxidative coupling with stoichiometric oxidant (e.g., FeCl3,
DDQ, etc.), Scholl conditions (AlCl3 or AlCl3/NaCl), or
photocyclization (Mallory reaction), although several other
approaches have also been explored, such as radicalanion
coupling (Schemes 9, 10, 29, 32, 130; 44.18), catalytic
dehydrogenation (44.1921, 136.12), coupling of aryllithiums
(164.3), or surface-assisted dehydrogenation (e.g., Schemes 14,
19). The latter method is not suitable for bulk synthesis but is
of increasing importance because of its applications in
nanoribbon chemistry.
The prototypical dehydrogenative annulation couples two
benzene rings, but direct couplings of heterocyclic rings can
also be achieved, for example, of pyrrole, imidazole, triazole,
thiophene, pyridine, pyrazine, and pyrimidine (cf., Schemes 4,
5, 11, 18, 20, 23, 25, 26, 27, 69, 102, 116, 122, 173, 206, 207,
208, 294). Ringsubstituent dehydrogenative couplings are
also possible (e.g., 3.78, 60.4; Scheme 199). The feasibility of
these reactions strongly depends on the properties of the units
being coupled, and electron-donating substituents on the rings
are usually required to ensure sucient reactivity and
selectivity. Competing processes may involve intermolecular
couplings (Scheme 20). Most typically, a CC bond is formed,
although other bond types can also be obtained (e.g., CB,
Scheme 17; CN, 43.7; NN, 43.4; CO, 90.2, 98.7,
Schemes 96, 97; CS, 99.2). The new ring, which may be
carbo- or heterocyclic, is usually six-membered, although ve(196.4, 197.3; Charts 59, 60; Schemes 263, 264, 273, 275,
276), seven- (Schemes 13, 156, 157, 186), and eight-membered
rings (Scheme 162; 158.8, 164.3, 206.8, 268.3) have also been
prepared. Nevertheless, when rings other than 6-membered are
targeted, rearrangements may occur (cf., 33.3). The feasibility
of closing a particular ring size is at least in part determined by
the internal strain of the resulting fused ring system.
One of the principal advantages of the dehydrogenative
annulation approach is the possibility of performing tandem
annulations on aromatic oligomers, in which several (often six
or more) bonds are created at one time. Usually, the individual
annulations are topologically independent (i.e., they can in
principle be performed in any sequence), although zipper-like
multiannulations can be designed in appropriately large
precursors (e.g., 32.12, 58.2). Couplings inside macrocycles
are also possible (53.12, 124.8, 252.1, C70.3). Dehydrogenative annulations are typically intramolecular, because intermolecular variants usually suer from poor regioselectivity (cf.,
Scheme 33). Nevertheless, fairly selective intermolecular
couplings are occasionally reported, but the yields of such
reactions are usually moderate (43.2, 44.23, 50.3, 61.2,4, 62.3,
C14.1). Rings other than six-membered are rarely obtained in
this way, a notable example being the porphyrinacetylene
coupling leading to dehydropurpurin (Scheme 255).
1.4.2. Other Direct Annulations. Dehydrohalogenative
annulations (CH + CX, X = halogen, sulfonate) do not
involve a net change of the oxidation state of the substrate. The
coupling chemistry is typically based on metal-catalyzed Hecklike reactions (87.16, 131.2, 144.8; Schemes 152, 180; see
192.6) and numerous macrocyclization reactions (see section

7.1).
Because of the involved complexity, building a PHA system
by incremental annulation is rarely employed. Exceptions from
this rule are found among total syntheses of naturally occurring
PHAs, which nevertheless tend to rely on tailored tandem
annulations (cf., Schemes 44, 131, 132, 133). The preferred
approach, which is usually more step-ecient, involves the
synthesis of an aromatic oligomer, usually directly linked (sp2 to
sp2), which can have a linear or branched topology. The
presence of cove and fjord regions in such oligomers
(Scheme 1, box A) provides convenient sites of further orthoand peri-annulation, making them especially useful in the
synthesis of very large PHAs. Diverse branched oligoaryls,
structurally analogous to hexaphenylbenzene, have been used
for the synthesis of coronenoid systems (section 2; for
examples of related precursors built around ve- and sevenmembered rings, see Schemes 152 and 185, respectively). The
use of linear oligomers is of importance, for example, in the
synthesis of rylene derivatives (section 3) and porphyrin tapes
(sections 7.2 and 7.3).
Because of the strategic role of macrocycles as reactive
building blocks, macrocyclization reactions (section 7) are
often performed at an early stage of the synthesis, and are
followed by subsequent ortho- and peri-annulation steps.
Nevertheless, macrocyclizations can result in branched orthofusion (e.g., Scheme 193) or actually create peri-fusion points
(Schemes 259, 269, 270, 271; section 7.7). peri-Annulations are
occasionally performed inside macrocycles, such as those
involved in porphyrinoid N-fusion chemistry (Scheme 273)
and in the fold-in syntheses (Scheme 166, see also 161.8,
124.6, 53.12, 252.1, 70.3). Typical macrocyclization reactions
reviewed in sections 7 and 6.1 involve electrophilic substitution
reactions (porphyrinoids), biaryl couplings (Suzuki, Schemes
227, 231, 235, 286; Stille, Scheme 232; Ullmann-type, Schemes
286, 287, 291, 292; Chart 69), and acetylene couplings
(Sonogashira, 288.3; Scheme 289; Chart 69; Glaser coupling,
Schemes 228, 230; 289.9; Chart 68). Glaser macrocyclizations
are often followed by a PaalKnorr conversion of the
diacetylene bridges to pyrrole or thiophene rings. Specic
classes of macrocyclic rings were also be constructed using
oxidative couplings (Schemes 236, 267; C63.11), olenation
reactions (McMurry, Schemes 265, 290; Chart 69; Wittig,
Scheme 290), and various nucleophilic reactions (Schemes 165,
269, 270, 286, 294, 296; Chart 67). Interestingly, certain
annulation reactions can be used for building macrocycles
(Scheme 293; 286.14).
The construction of peri-fusion points in PHA frameworks
can be achieved using diverse annulation methods. periAnnulations can be classied on the basis of their location in
the substrate molecule (zigzag, bay, cove, or fjord region) and
with respect to cyclization topology (direct, i.e., ring-to-ring,
ring-to-substituent, or intermolecular, Scheme 1, box A). Fjord
and cove regions can be annulated directly, producing,
respectively, six- and ve-membered rings. For zigzag and bay
regions, the inclusion of a substituent or an incoming reactant is
necessary to produce a ve-membered or larger ring. The most
successful and versatile peri-annulations are discussed below
and illustrated in Scheme 2.
1.4.1. Dehydrogenative (Oxidative) Annulations. This
general class of reactions is among the most versatile and
frequently used synthetic methods in PHA (and PAH)
chemistry. The transformation is typically of the direct type;
I
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40), sulfur, and selenium reagents (100.2, 107.11, 142.6,8,

Scheme 154). In the case of S and Se, the cyclizations can be
induced not only by using formally electrophilic reagents, but
also by direct reaction with elemental chalcogens (Schemes
168, 176; Chart 53).
Nucleophilic condensations are a diverse class of annulation
reactions, especially useful for the synthesis of hetero rings.
Such reactions were extensively used in the classical syntheses
of nitrogen-rich carcinogenic PHAs (e.g., Schemes 139, 140),
and in the later work on pyridoacridine alkaloids (Schemes 44,
131, 132) and heteratriangulenes (section 4.1). The most
important peri-annulation strategies include Schi-like condensations leading to pyridine (36.2,10, 87.3, 132.4, 211.3,
165.9, 287.7; Schemes 94, 140), pyridazine (Schemes 41, 42,
57, 94; 87.5), and pyrimidine rings (64.1; Schemes 92, 93, 139,
140). Pyridine or pyrylium rings can also be formed by
cyclization of ethynyl-substituted precursors (36.14, 37.89,
131.9; Scheme 94; for pyrylium-to-pyridine conversions, see
Schemes 56, 94). Seven-membered rings can also be closed in
nucleophilic condensations (146.3, Scheme 277), and a range
of bicyclic systems, such as quinoline (Schemes 65, 130, 201),
quinolizine (Scheme 30), 2,7-naphthyridine (8.3,5, 44.16,22,
131.15, 140.3; Scheme 133), 2,6-naphthyridine (83.3), or 1,6naphthyridine (141.2) have been assembled by means of
tandem bis-annulations.
Oxygen-containing rings can also be peri-annulated using
nucleophilic cyclizations. Acid-catalyzed condensations of 1,4naphtho- and 1,4-benzoquinones are instrumental in the
synthesis of tetraoxa[8]circulenes and related systems
(Schemes 159, 160). In cationic methoxyarenes, the OMe
groups become suciently labile to allow their ecient
nucleophilic displacement, which is a key step in the syntheses
of heteratriangulenes and heteracirculenes (Schemes 77, 78, 79,
80, 101; 135.4). Substitution of phenol/quinone functions is
also usable for the synthesis of 1,2-dithiole rings (Scheme 144)
and annulated oxepins (Scheme 188; 189.16).
In addition to the above condensations, which typically
involve the release of water or alcohol, nucleophilic substitution
of haloarenes and aryl sulfonates can be eected under either
base-promoted or catalyzed (Pd, Cu) conditions. This reactivity
enables the synthesis of 5-membered (61.9, C52.8, 279.5,
281.2; Schemes 163, 283), 6-membered (Schemes 76, 81, 132,
138, 140, 142, 163, 213; 147.2), and 7-membered heterocycles
(186.8, 189.6,10, Schemes 283, 274; see also 272.5).
Zigzag-region annulations create a single additional perifusion point and are often achieved using electrophilic or
nucleophilic chemistry (for an additional example of a
nucleophilic benzannulation, see 217.3). Further cyclization
strategies specic to the zigzag region are represented by [3+2]
and [3+3] cycloadditions of azomethine ylides (Schemes 126,
152; Chart 42) and other systems (Scheme 181), and by
transformations involving cumulene or acetylene substituents
(178.2, 179.4).
Ring-to-ring transformations are occasionally used for
elaborating fused PHA frameworks. Examples of ring rearrangements employed for this purpose include a transamidation used
in the synthesis of triazasumanenes (155.3), formation of
azepinone dyes from indigo (Scheme 184), conversion of 1azatriptycene into azepines (Scheme 185), GraebeUllmann
synthesis of pyridine rings from triazoles (136.25), and an
unusual rearrangement of spiro-porphodimethenes into peripherally fused porphyrins (264.1). Cycloadditioncycloreversion
sequences can be used for remodeling of existing rings (130.4).
137.10 for a tandem process involving an initial Heck-type

step), and less frequently on radically induced (Schemes 31,
82), thermal/base promoted (Scheme 85), or electrochemical
couplings (144.5). In addition to six-membered rings, which
are most typically formed, closures of ve- (180.2,17, 189.4,
217.4, 256.2, Schemes 257, 258, 262) and seven-membered
rings (182.6,7, 183.6, 186.10) have been reported. Reductive
annulations are typically performed using Ullmann-type
couplings, notably the Ni0-based Yamamoto method, which is
valuable for its ability to introduce internal strain to the fused
ring systems. Examples of such reductive cyclizations include
intramolecular formation of 6-membered (Schemes 166, 173)
and larger rings (Schemes 286, 287, 291, 292; Chart 69), and
an intermolecular benzannulation (61.6). An intermolecular
annulation was induced under McMurry conditions (Scheme
35).
1.4.3. Bay-Region Cyclizations. Annulations in bay
regions enable lateral expansion of perylenoids, providing
access to coronene and benzo[ghi]perylene analogues (sections
2 and 3). The classical synthesis of Cibalackrot (175.2) can be
seen as a double bay annulation of indigo. Even though bay
regions in aromatic systems are typically unreactive as dienes in
cycloaddition reactions, combining a (formal) DielsAlder step
with dehydrogenation is possible with some reactants, leading
to benzene rings (from maleic anhydride: 3, 47.3, Scheme 157;
see also 180.17) or pyridazine rings (from azodicarboxylates,
Schemes 8, 9, 10; from 4-phenyl-1,2,4-triazoline-3,5-dione,
Schemes 9, 10, 34, 57). Intermolecular benzannulations of bay
regions were also achieved by using catalytic cyclization of
acetylenes (Schemes 143, 161) or conversion of nitroarenes
into 1,2-dithiines (Scheme 57). Bay regions can be alternatively
annulated using various intramolecular substituent-to-ring
cyclizations, such as the PictetSpengler reaction (Scheme 7)
or FriedelCrafts cyclizations (see below). Bay-region
cyclizations of ethynyl (Pt-catalyzed, 45.34, 95.4; InCl3catalyzed, 143.7) and nitrile substituents (Scheme 55) have
also been reported. An intramolecular cycloaddition of a
ketenimine was used for a tandem assembly of a quinoline
subunit (136.9). Five-membered rings, such as pyrrole or
thiophene, can also be closed in bay regions, using various
synthetic approaches (Schemes 21, 46, 54, 158; Chart 54; 53.6,
53.8, 174.2).
1.4.4. Electrophilic Condensations. peri-Annulations
based on FriedelCrafts alkylation or acylation are highly
useful in the synthesis of six-membered rings (Schemes 56, 70,
72, 75, 82, 97, 107, 125, 127, 134, 137, 143, 144, 179, 202, 217,
218, 220, 224, 225, 226, 241), but are also applicable for closing
ve-membered (Scheme 50) and seven-membered rings
(Schemes 12, 187), as well as macrocycles (notably porphyrin
analogues). In alkylations, the direct cyclization product
typically requires an aromatization step, such as dehydrogenation (e.g., in pyrrolealdehyde condensations, section 7),
dehydration (32.6, 88.3,8), or reductive dehydroxylation (37.2;
Scheme 89), whereas acylations may lead to the aromatic
product via spontaneous tautomerization (e.g., 36.8). Sixmembered (90.5, 97.7, 144.11, 180.2,12) and sevenmembered rings (185.2) can be obtained via electrophilic
cyclization of diazonium salts. peri-Fused pyridine rings have
been formed via cyclization of nitrene intermediates (209.2,
210.2, 136.10; Scheme 212).
Heteroatom bridges can also be introduced using electrophilic substitutions of CH, CSi, or CM bonds, with boron
(Schemes 15, 16, 39, 45, 57, 95), phosphorus (Schemes 29,
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containing nitrogen or oxygen atoms are discussed in section

2.1. Section 2.2 discusses the emerging chemistry of pyrrolefused coronene systems, which are rare examples of internally
doped azacoronenes (for triangulene derivatives containing an
internally aza-doped coronene framework, see Scheme 71 in
section 4.1). Our own work on peripherally expanded
azacoronenes is discussed here for consistency, even though
these systems are strictly classied as perylenoids. In section
2.3, we summarize recent advances in the chemistry of B- and
BN-doped heteracoronenes. Recent advances in the eld of B
and BN aromatics have been reviewed by the groups of
Ingleson,25 Piers,60 and Liu.61 Sections 2.4 and 2.5 discuss
heteroatom-free coronenes that contain, respectively, peri- and
ortho-fused heteroaromatic moieties.
Rare examples of ring contractions, such as the extrusion of

sulfur from thiepines (36.2, 87.2, 128.2, 189.6) or contraction
of imides to lactams (61.7), have also been reported.
2. CORONENOIDS
The term coronenoid will be used throughout this Review to
describe all systems containing the seven-ring framework of
coronene. The rst heteroaromatic coronene derivatives were
reported in the 1950s (compounds 22.3 by Zinke et al.54 and
6.4 by Clar et al.55). In recent years, the interest in
nanographene chemistry has produced a range of extended conjugated systems, many of which contain heterocyclic rings.
Recent advances in nanographene synthesis were reviewed by
Yan and Li,56 Tran-Van and Wegner,57 Wu and co-workers,58
and the Mullen group.8 An account of the chemistry of
contorted polycyclic aromatics was published by Nuckolls and
co-workers.59 While the above reviews are largely focused on
carbocyclic structures, this section is focused strictly on
heteroaromatic derivatives. For convenience, these systems
are classied as follows (Chart 4). Edge-doped heteracoronenes
2.1. Edge-Doped Aza- and Oxacoronenes
2.1.1. Diazacoronenes. The rst successful synthesis of

the unsubstituted 1,2-diazacoronene 3.1 was carried out by
Tokita et al. in 1982 (Scheme 3).62 In the rst step, 1,2diazacoronene-7,8-dicarboxylic anhydride 3.3 was prepared in
the reaction between the 1,2-diazabenzo[ghi]perylene derivative 3.2 and maleic anhydride in the presence of chloranil. In
the next two steps, the hydrolysis of compound 3.3 was
performed, and the resulting compound 3.4 was heated with
soda lime to yield 3.1. 1,2-Diazacoronene, poorly soluble in
common organic solvents, had a yellow color and an electronic
spectrum similar to that of coronene.
Substituted Schi base diazacoronenes were synthesized in
2012 by Cheng, Xiao et al. (Scheme 3).63 Two isomeric
derivatives, 1,7-diaza- 3.7 and 1,8-diaza- 3.8, were prepared in a
photocyclization reaction between bisaminoperylene tetraesters
and butyraldehyde and were modied further without
separating them. In subsequent steps, these coronenes were
converted into anhydride (3.9/3.10) and diimide (3.11/3.12)
derivatives. The diimides 3.11/3.12ab show absorption
largely independent of substitution and are uorescent, with
emission maxima at around 477 nm and extremely small Stokes
shifts of only 24 nm. Electrochemical data revealed that these
compounds could accept up to two electrons and might be
usable as n-type semiconductor materials. Because of the low
solubility of 3.11b/3.12b, the self-assembly behavior and
Chart 4. Classication of Coronenoids Used in This

Sectiona
-Conjugation and possible additional fused carbocyclic rings are not

indicated.
a
Scheme 3. Synthesis of Diazacoronenes and Schi-Base Diazacoronenesa
Reagents and conditions: (a)62 chloranil, maleic anhydride, 20 min, reux; (b) benzyl alcohol, NaOH, 30 min, 100 C; (c) soda lime, powdered, 1 h
at 320 C, then 2 h at 350 C; (d)63 butyric aldehyde, cat. I2, 6 h, 62 C; (e) chlorosulfonic acid, 4 h, rt; (f) amine, 4 h, 115 C, Ar atmosphere.
a
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Scheme 4. Synthetic Routes to Diimide Diazacoronenes and Thiophene Fused Azacoronenesa
a
Reagents and conditions: (a)64 h, 3 h; (b) h, 6 h; (c)65 K2CO3, 18-crown-6 cat., 2-ethylhexyl bromide, DMF, overnight, 120 C, N2 atm; (d) h
with a 300 W incandescent lamp, I2, 36 h; (e) NBS, chloroform, overnight; (f) Pd(PPh3)4, toluene, DMF, 24 h, 100 C, N2 atm; (g) n-BuLi in
hexanes, THF, 30 min, 0 C, then 1 h, rt, then 0 C, trimethyltin chloride in hexanes, overnight, rt; (h) Pd2(dba)3, P(o-Tol)3, toluene, overnight, 100
C, then bromobenzene, 3 h, then tributylstannyl thiophene, 3 h.
photocyclization was used to produce thienoazacoronenes 4.7a

and 4.7b, which were converted into the functionalized
dibromo and distannyl derivatives 4.8a and 4.8b, respectively.
The latter functionalized 4.8 were subjected to the Stille
coupling reaction, leading to the thienyl monomer 4.9a and
polymer 4.9b. The 4.7a derivative showed a high degree of selforganization in solution and in the bulk, both in the crystal and
as spuncast thin lms. Thin-lm eld-eect transistors exhibited
an average and maximum hole mobility of 0.0013 and 0.028
cm2 V1 s1, respectively. These mobilities were lower than
those of high-performing acenes and thienoacenes, but were
nevertheless 1 order of magnitude higher than observed for
hexathienocoronenes and were among the top eld-eect
mobilities for solution-processed discotic materials. Organic
photovoltaic devices using a thieno-fused diazacoronenecontaining conjugated polymer as the donor material had a
high open-circuit voltage of 0.89 V, indicating the potential use
of this coronene analogue as a low-HOMO electron donor for
tuning the energy levels in the hole transporting system.
In 2015, Liu and co-workers reported the synthesis of benzoand thieno-fused azacoronene derivatives (Scheme 5).66
Dichlorodiazaperylenes 5.1 or 5.4 were diversely functionalized
at the -pyridine positions to produce alkoxy- (5.2a and 5.5a),
thioalkyl- (5.2b and 5.5b,c), alkyl- (5.2c), or aryl-substituted
(5.2d) derivatives, all of which underwent oxidative dehydro-
charge-carrier mobility were studied only for 3.11a/3.12a. Both

derivatives showed self-assembly into ordered nanobelts. The
charge-carried mobility was investigated using the steady-state
space-charge-limited current (SCLC) technique. The mobility
level for 3.11a/3.12a reaches 5.65 104 cm2 V1 s1 at an
electric eld of 0.3 MV cm1, which is the average level of
SCLC mobility observed for perylenediimides (PDIs).
Structurally related diimide analogues containing fused
imidazole (4.2) and 1,2,4-triazole rings (4.4) embedded as
functional constituents were obtained in 2006 by Li at al.64
These compounds were obtained through photocyclization
reactions of doubly substituted precursors 4.1 and 4.3,
respectively (Scheme 4). The electron-donating and -accepting
nature of the -system in 4.2 and 4.4, respectively, was reected
in the self-assembly capabilities of these molecules. Compound
4.2 formed one-dimensional nanostructures stabilized by strong
stacking interactions, in contrast to the -electron-poor
4.4. These observations indicated the potential to control the
self-assembly of -extended PDI cores, by appropriate selection
of fused heterocyclic rings.
Thieno-fused diazacoronenes (4.79), substituted with
peripheral alkoxyl groups, were described by Liu and coworkers (Scheme 4).65 The critical step of the synthesis was the
simultaneous O-alkylation/aromatization process leading to
azaperylenes 4.6a and 4.6b. In the next step, an iodine-assisted
L
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(red) and 6.3 (blue). The absorption spectra of 6.2, 6.3, and
6.1 revealed that consecutive ring closures had limited inuence
on absorption bands in the ultraviolet range, while causing
strong red shifts of the lowest energy bands (max = 576, 660,
and 732 nm, respectively).
In 2014, Gryko, Cywinski et al. reported the synthesis of a
structurally related -expanded coumarin.67 This new system,
dibenzo-1,7-dioxacoronene-2,8-dione 6.6, which can also be
viewed as a -expanded pentacene derivative, was obtained by a
double intramolecular oxidative coupling of the 3,9-dioxaperylene-2,8-dione derivative 6.5 (Scheme 6). Two oxidation
methods were employed: irradiation in the presence of air and
iron(III)-mediated oxidation. Both methods were regioselective, leading to the product with lower steric hindrance,
providing yields of 54% and 87%, respectively. Compound 6.6
shows the lowest-energy absorption at 520 nm, and the
uorescence emission at emmax = 571 nm (F = 0.90), which
are both red-shifted and more intense in comparison with the
incompletely fused coumarin analogues.
2.1.3. Triazacoronenes. In 2010, a range of substituted
1,5,9-triazacoronenes 7.2ah were obtained by Wei et al. in a
3-fold PictetSpengler reaction followed by spontaneous
oxidative aromatization.68 This tandem reaction results in the
insertion of a methylidyne group between each nitrogen atom
and the adjacent benzene ring in compound 7.1, to build three
isoquinoline motifs (Scheme 7). The reaction proceeds with a
range of aldehydes, both aromatic and aliphatic, in the presence
of triic acid. All 7.2ah derivatives are soluble in common
organic solvents and show high thermal stability (above 300
C). Their absorption maxima are red-shifted in comparison
with the all-carbon analogue, 1,2,5,6,9,10-hexamethoxycoronene, and have higher values of their molar extinction
coecients. The HOMO energy levels (6.0 eV) are also
lower than those of the all-carbon analogue (5.5 eV),
suggesting that 7.2ah constitute intrinsic n-type semiconductors with good hole-blocking and electron transport
properties. These 1,5,9-triazacoronenes produced strong
electrogenerated chemiluminescence (ECL) emission for
radical ion annihilation, by stepping from the rst oxidation
wave to the reduction wave. Subsequent extension of the above
synthetic approach yielded derivatives 7.3 devoid of methoxy
groups, in particular the parent unsubstituted 1,5,9-triazacoronene.69
2.1.4. Tetraazacoronenes. In 1972, Hurley, Dutt, and
Marvel reported the synthesis of a 1,4,7,10-tetraazacoronene
derivative 8.3 (Scheme 8).70 The initial acid-catalyzed
Scheme 5. Synthesis of Peripherally Functionalized

Diazacoronenesa
a
Reagents and conditions: (a)66 (1) NaH, N2 atm, 2-ethylhexan-1-ol,
DMF, 0 C, (2) overnight, rt; (b) K2CO3, 2-ethylhexyl-1-thiol, cat. 18crown-6, N2 atm, DMF, overnight, 120 C; (c) (1) (2-ethylhexyl)
magnesium bromide, Ni(dppp)Cl2, THF, N2 atm, 2 h, 0 C, (2)
overnight, reux; (d) 2-(4-((2-octyldodecyl)oxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, K2CO3, Pd(PPh3)4, Aliquat 336, toluene,
48 h, 120 C; (e) cat. I2, 300 W incandescent lamp, chloroform, 24 h;
(f) cat. I2, 300 W incandescent lamp, benzene, 24 h; (g) K2CO3, 2decyltetradecyl-1-thiol, cat. 18-crown-6, N2 atm, DMF, overnight, 120
C.
genations, yielding compounds 5.3ad and 5.6ac. These

azacoronenes displayed signicant changes of their absorption
and uorescence spectra upon protonation, suggesting their
potential use as naked-eye dual-mode probes for protons.
2.1.2. Dioxacoronenes. The extended 1,7-dioxacoronene
system 6.4 (Scheme 6) was reported by Clar et al. in 1956.55
The green compound 6.4 was prepared by self-condensation of
dinaphthyloxyanthraquinone 6.1 in a sodium chloride
aluminum chloride melt at 175180 C. By reacting the
same starting material at lower temperatures, it was also
possible to isolate the partially coupled dioxaperylenoids 6.2
Scheme 6. Synthetic Routes to Dioxacoronene Derivativesa
Reagents and conditions: (a)55 NaCl, AlCl3, 10 min, 180 C, then 15 min, 145 C; (b) NaCl, AlCl3, 10 min, 175 C; (c) NaCl, AlCl3, 35 min, 175
180 C; (d)67 h (365 nm), THF, 24 h, rt; (e) FeCl3, dry DCM, cat. BF3Et2O, 30 min, rt.
a
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1,2,4-triazoline-3,5-diones as dienophiles.7479 The utility of

this approach was tested with 3,9- and 3,10-dihexylperylene, to
yield the isomeric tetraazacoronenes 9.5 and 9.11 (Scheme 9),
and with N-substituted perylenedicarboxyimide (to yield
9.1278). The rst approach to 9.5, proposed by Mullen, Spiess,
and co-workers in 1993,74 and subsequently rened,79 started
with the coupling reaction of 1-bromonaphthalene in the
presence of thallium triuoroacetate. Next, the resulting 4,4dibromo-1,1-binaphthyl 9.2 was converted into the dialkyl
derivative 9.3, which was reductively fused and following
oxidative rearomatization gave the substituted perylene 9.4.
The nal product 9.5 was obtained in the 2-fold DielsAlder
reaction with N-alkyltriazolinediones. An alternative method,
which obviates the use of thallium salts but suers from poor
regioselectivity,77 starts with a 2-fold bromination of perylene,
which leads to an inseparable 1:1 isomeric mixture of 3,9- and
3,10-dibromoperylenes. The isomer mixture was subjected to
the Hagihara coupling reaction, and the alkyne derivatives were
catalytically hydrogenated. The nal product was obtained in
the same manner as in the rst method. Both methods allow
one to obtain variously substituted analogues of 9.5 and 9.11.
All of these systems are blue solids with an absorption
maximum at 585 nm.79 The triazolinone rings in 9.5b could be
cleaved by treatment with NaOH at temperatures above 90 C,
followed by acidication, yielding the readily soluble
tetraazacoronene 9.6.74
Depending on the R1 and R2 chain lengths, the 9.5 systems
form liquid-crystalline phases of either hexagonal discotic or
smectic type, and a similar mesomorphic behavior is also
observed for isomer mixtures.74,75,77,79 In subsequent work,
oligomeric systems such as 10.3 and 10.6 were developed and
shown to reproduce the general mesomorphic characteristics,
while showing variations of the dynamic properties of the LC
phase (Scheme 10).76 Strict hexagonal order was also observed
in the discotic phases formed by the T-shaped mesogen 9.12
and related derivatives.78
Scheme 7. Synthesis of 1,5,9-Triazacoronenesa
Reagents and conditions: (a)68 aldehyde, DMF, 1% triic acid, 100

C (for aromatic aldehydes) or 40 C (for aliphatic aldehydes).
condensation of 8.1 and 8.2 apparently produced an

incompletely fused intermediate, which upon further heating
in vacuum was converted into a highly insoluble product, to
which the structure 8.3 was assigned on the basis of elemental
analysis and IR spectroscopy. In an extension of the above
synthesis, a condensation of 8.1 and the tetraketone 8.4 was
attempted, again combining acid-catalyzed and thermal steps.
While no structural proof was provided for the expected laddertype structure 8.5, the work is one of the rst attempts at the
controlled synthesis of heteroatom-doped graphitic nanoribbons (for a slightly earlier example, 110.7 by Stille and
Mainen,71,72 see section 4.6).
In 1982, Tokita and co-workers reported a synthesis of
1,2,7,8-tetraazacoronene 8.7, analogous to the preparation of
3.1 described above.73 The heptacyclic framework was
constructed by a double DielsAlder reaction between
perylene and diethyl azodicarboxylate, to produce the tetraester
8.6. The ester groups in the latter species were then saponied
and decarboxylated, with concomitant oxidation of the NN
bonds, providing the bis(pyridazino)-fused perylene derivative
8.7.
The DielsAlder strategy of Tokita et al. was subsequently
extended by the Mullen group, who employed substituted
2.2. Pyrrole-Fused Azacoronenes
Hexapyrrolohexaazacoronene (HPHAC, Scheme 11) is the

prototypical example of an emerging class of nanographenes
containing peri-fused pyrrole rings (Chart 5). In an initial study
by Jouini et al. in 2003,80 the synthesis of 11.2a by oxidation of
hexapyrrolylbenzene 11.1a was attempted in the presence of
iron(III) perchlorate. Only products of partial coupling of
11.1a were observed using MALDI-TOF mass spectrometry,
Scheme 8. Synthetic Routes to Tetraazacoronene Derivativesa
Reagents and conditions: (a)70 (1) DMA, AcOH, 160 C, 10 h; (2) vacuum, 200 C, 10 h; (3) vacuum, 350 C, 10 h; (b) (1) PPA; (2) vacuum,
200250 C, 20 h; (3) vacuum, 300 C, 10 h; (4) vacuum, 350400 C, 10 h; (c)73 DEAD, neat, 160 C, 6 h; (d) NaOH, benzyl alcohol, 90100
C, 30 min.
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Scheme 9. Synthetic Routes to 1,2,7,8-Tetraazacoronenes Containing N-Substituted 3,5-Dioxotriazoles Unitsa
a
Reagents and conditions: (a)79 thallium triuoroacetate, TfOH, 3 h, rt, Ar atm; (b) Ni(dppe)Cl2, butylmagnesium bromide, ether, 18 h, reux, Ar
atm; (c) K, dimethoxyethane, dark, 2 days, rt then oxygen atm, 1 day; (d)78,79 N-heptadecyltriazolinedione, m-xylene, reux; (e)74 NaOH, benzyl
alcohol, 90 C; (f)77 Br2, AcOH, 40 C, 1 h, then 50 C, 5 h; (g) piperidine, 1-hexyne, Pd(PPh3)4, CuI, THF, 80 C, 14 h; (h) Pd/C, THF, H2, rt.
Scheme 10. Synthetic Routes to 1,2,7,8-Tetrazazcoronene Polymersa
a
Reagents and conditions: (a)76 magnesium turnings, 1,10-dibromodecane, ether, 1 h, reux, then Ni(dppe)Cl2, 2 h, rt, then 48 h, reux; (b) K,
dimethoxyethane, dark, Ar atm, 5 days, rt, then 1:1 mixture oxygennitrogen, 1 h, rt; (c) -deuterated N-heptadecyltriazolinedione, xylene, 3 min,
reux; (d) -deuterated didodecyl perylene, N-(ethoxycarbonylmethylene)triazolinedione, xylene, 3 min, reux; (e) 1,10-decanediol, xylene, 120 C,
Ti(O-i-Pr)4, 2 h, reux, Ar atm, then solvent removed in vacuo, pressure 103 bar, 200 C, 6 h.
Jouini et al.82 11.2a was obtained as a soft homogeneous thin

lm on the electrode surface after electrochemical oxidation in
organic media. In situ electrochemicalESR measurements
revealed that this lm underwent reversible oxidation processes
and was highly paramagnetic. The lm also showed a
continuously tunable spin concentration from 0 to 1 per
charge at room temperature by controlling the electrochemical
potential.
In a subsequent study by Mullen and co-workers, published
in 2007, a -aryl substituted HPHAC, 11.2d, was synthesized
and structurally characterized in its neutral and oxidized
presumably because of the low solubility of 11.2a in organic

solvents. In contrast, the oxidation of 11.1b, possessing
solubilizing octyl groups, led to a soluble product, with a
mass spectrum consistent with complete peripheral coupling.
The expected product, 11.2b, which likely formed as a mixture
of regioisomers, was not investigated further. The oxidation of
hexapyrrolylbenzenes was shown to proceed according to the
radical cation/substrate mechanism, in contrast to oxidative
polymerizations of pyrroles, for which dimerization of radical
cations normally occurs. The electrosynthesis and magnetism of
11.2a were subsequently explored by Lazerges et al.81 and
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Chart 5. Pyrrole-Fused Azacoronene Derivatives84
Scheme 11. Synthesis of Annularly Fused

Hexapyrrolohexaazacoronenesa
Reagents and conditions: (a)80 Fe(ClO4)3, MeCN; (b)83 (1)

CH3NO2/FeCl3, DCM, 1 h, rt; (2) N2H4.
dicationic states.83 11.2d was obtained by cyclodehydrogenation of the appropriate hexapyrrolylbenzene in the presence of
iron(III) chloride, followed by quenching with hydrazine. The
unsubstituted 11.2a was identied using MALDI-TOF, in
contrast to Jouinis work, whereas the mass spectra of the
expected dodecabromo derivative 11.2c were consistent with
partial debromination of the oxidized product. The molecular
structure of 11.2d was conrmed by single-crystal X-ray
diraction, showing the HPHAC core to be completely planar,
with the centers of the peripheral phenyl groups forming a
wavelike pattern above and below the molecular plane. In
contrast, DFT calculations predicted a bowl-shaped structure
for 11.2a, arising from the tight annular fusion of the vemembered rings. Compound 11.2d exhibited uorescence at
570, 617, and 673 nm, bathochromically shifted relative to
HBC, which uoresces at much shorter wavelengths (max =
465, 484, 492, 517, and 528 nm). Electrochemical measurements revealed four reversible one-electron oxidation steps for
11.2d. Chemical oxidation with antimony pentachloride
produced consecutively the radical monocation 11.2d+ and
dication 11.2d2+. The oxidation could be reversed by addition
of tetrabutylammonium iodide to the cationic forms. Structural
data obtained for the dication, as well as NICS calculations,
were consistent with the overall aromaticity of the oxidized
HPHAC core.
In 2013, HBCHPHAC hybrids were prepared by Takase,
Mullen, Nishinaga et al., using analogous oxidative coupling
reactions performed on mixed pyrrolearene precursors.84 The
introduction of two alkoxy groups at the meta positions of the
peripheral phenyl substituents was found to eectively promote
the oxidative coupling of precursors, leading to the complete
closure of the peripheral circuit. In this way, pentaaza-,
tetraaza-, and triazacoronene derivatives C5.1ac, C5.2ac,
and C5.3ac were obtained (Chart 5). Stepwise replacement
of pyrroles with dialkoxybenzene rings was found to drastically
alter the optical properties of the hybrids. As in the parent
HPHAC system, lowest-energy electronic transitions are
partially allowed for C5.1a3a, with a 10-fold increase of
extinction coecients recorded for C5.3a in comparison with
C5.1a2a. All compounds exhibited colorful uorescence
emissions, the color changing from red through yellow, deep
red, to green as the number of pyrrole rings decreased from
11.2d to C5.1a3a. X-ray crystal structures obtained for the
neutral states of C5.3b and C5.4a conrmed the planarization
of the azacoronene core. Observation of uorescence and

phosphorescence at both room temperature and 77 K allowed
one to estimate the small S1T1 gaps (EST < 0.36 eV).
Dications of hexaazacoronene 11.2d and pentaazacoronene
C5.1a exhibited a closed-shell character, whereas open-shell
congurations were predicted for tetraazacoronene C5.2c and
triazacoronene C5.3c dications on the basis of theoretical
calculations.
A family of expanded hexapyrrolohexaazacoronenes 12.3 and
12.6 containing up to two saturated bridges at the periphery
were reported in 2014 by Step ien et al.85 The expansion of the
peripheral circuit of these nanographenes was achieved by
introducing additional carbon bridges between the pyrrole
subunits. 12.3 and 12.6 were synthesized from substituted
hexapyrrolylbenzenes using a two-step condensationaromatization procedure (Scheme 12). In the rst step, compound
12.1 was reacted with p-nitrobenzaldehyde, to yield consecutively two bridged species: 12.2 and 12.4. DDQ-mediated
oxidative coupling of 12.2, followed by reductive workup with
aqueous hydrazine, led to the product 12.3. In the case of the
more congested 12.4, oxidation with DDQ, followed by acidic
workup, yielded a monocationic species isolated as the
tetrauoroborate salt, [12.5][BF4]. In contrast to 12.3,
possessing a saturated benzylidene bridge between two
pyrroles, cation [12.5]+ contained one fully conjugated sevenmembered ring. Steric eects had an inuence on the
nucleophilic additions to the 12.5 cation, enabling stereocontrolled syntheses of cis- and trans-12.6. The oxidative
dehydrogenation of benzylidene bridges in 12.3, [12.5]+, and
stereoisomers of 12.6 was found to be stereochemically
controlled: it was kinetically hindered in the prevailing endo
arrangement of the sp3 bridges but proceeded easily for the exooriented sp3 bridges. Despite the interrupted conjugation on
the periphery, expanded azacoronenes had easily accessible
higher oxidation levels. The electrochemical analysis of the
bridged systems revealed up to six (for cis-12.6) oxidation levels
and up to one (for [12.5]+) reversible one-electron reduction
of the central -conjugated system. For cis-12.6, a diamagnetic,
quadruply charged species was chemically generated by reaction
with SbCl5. Oxidized forms of expanded hexapyrrolohexaazacoronenes show extensive -electron conjugation and are
ecient UVvisNIR absorbers, active up to ca. 2400 nm. In
P
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Scheme 12. Synthetic Routes to Expanded Hexapyrrolohexaazacoronenesa
a
Reagents and conditions: (a)85 p-nitrobenzaldehyde, BF3Et2O, DCM, rt, 1 h; (b) (1) DDQ, DCM, rt, 1 h, (2) H2O, (3) N2H4; (c) pnitrobenzaldehyde, BF3Et2O, chloroform/EtOH, rt, 1 h; (d) (1) DDQ, DCM, rt, 2 h, (2) H2O, (3) 12% HBF4 (aq); (e) NaCN, THF, DMF, N2
atm, rt, 1 h; (f) Na2CO3, DCM, MeOH, rt, 1 h; (g) NaBH4, THF, N2 atm, rt, 1 h; (h) (1) N2H4, DCM, rt, 5 min; (2) CuSO4, DMF, rt, overnight.
Scheme 13. Synthesis of a Peripherally Conjugated 5-6-7 Nanographenea
Reagents and conditions: (a)86 Ag2CO3, Pd(OAc)2 cat., pentauorobenzene, DMF, dimethylsulfoxide, 120 C; (b) (1) NaH, diarylpyrrole, DMF,
ice bath, (2) 13.2a or 13.2b, 50 C; (c) BAHA, diethyl ether, THF, rt; (d) Zn amalgam or Zn powder, DCM or chloroform-d; (e) BAHA,
[NO][SbF6] or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, DCM or MeCN; (f) BAHA, diethyl ether, THF, rt.
a
the doubly oxidized species [12.6]2+, a tendency toward

biradicaloid electron conguration was indicated by computational data.
In 2015, Step ien and co-workers prepared heteroaromatic 56-7 nanographenes, containing an assembly of ve-, six-, and
seven-membered rings (Scheme 13).86 The oxidative coupling
of an indole-containing precursor 13.3a (Scheme 13), using 12
equiv of tri(4-bromophenyl)ammoniumyl hexachloroantimo-
nate (BAHA) as the oxidant, led directly to a dicationic 5-6-7

nanographene [13.4a]2+, which was isolated as a hexauoroantimonate salt. Interestingly, the reaction with BAHA
strongly favored the formation of [13.4a]2+, and small amounts
of the salt could be isolated even when 2 equiv of the oxidant
was used. [13.4a][SbCl6]2 was quantitatively converted to the
neutral species 13.4a by reduction with zinc amalgam. When
the benzyl-substituted derivative 13.3b was subjected to the
Q
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Scheme 14. Synthesis of B-Doped Nanographenes and GNRsa
Reagents and conditions: (a)87 (1) 9-bromo-bis(mesityloxy)anthracene, n-BuLi, Et2O, 1 h, from 0 to 25 C, (2) 14.1, toluene, 12 h, from 0 to 25
C; (b) FeCl3, CH3NO2, DCM, 40 min, 0 C; (c)89 Au(111) surface, annealing at 180 C; (d) Au(111) surface, annealing at 400 C; (e) Au(111)
surface, annealing at 510 C.
Ullmann-type step, performed by annealing the monomer

14.4 on an Au surface at 180 C, the corrugated polymeric
precursor 14.5 was obtained. The latter species was subjected
to surface-assisted dehydrogenation at 400 C, to yield
completely at nanoribbons of the general structure 14.6
(ribbon width N = 7). Further annealing at 510 C led to the
fusion of the armchair edges of 14.6, producing nanoribbons
with N = 14 (e.g., 14.7) and N = 21, characterized by variable
alignment of boron-doped sites. The Lewis acidity of the Bdoped sites in the nanoribbons was demonstrated by selective
adsorption of nitrous oxide (NO) molecules.
2.3.2. BN-Embedded Systems. Tetraheteracoronenes
15.3a,b containing two embedded BN fragments were
described by Cao, Wang, Pei et al.90 In addition to the BN
units, these ring systems contained four ortho-fused thiophene
rings. They were synthesized in three steps, beginning with
6,13-dihydro-6,13-diazapentacene, which was converted into
the tetrabromo derivative 15.1 and subjected to a Stille
coupling reaction with tributyl(5-alkylthiophen-2-yl)stannanes.
Next, electrophilic borylation was performed on the multiply
lithiated 15.2a and 15.2b, yielding the BN-embedded
heteracoronenes 15.3a and 15.3b (Scheme 15). The
introduction of BN units was found to modulate the molecular
geometries of the -conjugated heteracoronene core. The
assembly of two dierent conformers of 15.3b into sandwichlike 2:1 aggregates was observed by single-crystal X-ray
diraction, providing an example of a self-organization process
in a one-component system. Compound 15.3b exhibited
photoconductivity as the rst BN-containing -conjugated
species.
In 2015, Cao, Wang, Pei, and co-workers91 as well as Zhang
et al.92 independently reported the synthesis of 3,4,7,8,11,12hexamethoxy-1,5,9-triaza-2,6,10-triphenylboracoronene (16.2,
Scheme 16). In both reports, the ultimate BN ring closures
were achieved by reacting 2,3,6,7,9,10-hexamethoxy-1,5,9triaminotriphenylene with dichlorophenylborane in dry 1,2dichlorobenzene. In the solid state, 16.2 has a fully planar
geometry of the BN heteracoronene backbone. In comparison
with its all-carbon analogue, 16.2 showed blue-shifted
absorption and emission spectra. Compound 16.2 is unstable
in the presence of water because the BPh bonds are easily
same BAHA-induced oxidation, the outcome of the reaction

was dierent. The green precipitate that formed was found to
contain mainly the partly coupled product [13.5b][SbCl6]2,
which was cleanly reduced by zinc amalgam, to yield the
corresponding neutral species 13.5b. Near-infrared absorption
and emission properties of the nanographene core were
enhanced by peripheral expansion and ring fusion at all
oxidation levels. The dicationic states (13.4) showed distinct
aromaticity originating from a peripheral -conjugated circuit.
The partially coupled intermediate [13.5b][SbCl6]2, trapped in
the synthesis of the 5-6-7 nanographene, was explored as a
reference system, showing an unexpected reduction of the
optical band gap due to intramolecular charge transfer.
2.3. B- and BN-Doped Coronenes
2.3.1. Diboracoronenes. In 2012, Saito, Yamaguchi et al.

synthesized a stable coronene derivative 14.3, containing two
boron atoms in the core87 (Scheme 14; an incompletely
conjugated diboracoronene 82.8 is discussed in section 4.1).
Their synthesis started with the lithiation of 9-bromobis(mesityloxy)anthracene, followed by the addition of the
resulting lithio derivative to dibromodiborapentacene 14.1. The
intermediate thus obtained, 14.2, possessed bulky electrondonating mesityloxy substituents, which were introduced to
secure regioselectivity of the subsequent oxidation and to
prevent the strong aggregation in the nal product. The
cyclodehydrogenation of 14.2, performed with an excess of
FeCl3, proceeded successfully to form 14.3 in a 51% yield. 14.3
was isolated as a deep-purple solid, suciently soluble in
common organic solvents. 14.3 is a closed-shell system and is
an example of a structurally uniform boron-doped nanographene. Its electronic spectrum in solution showed the
presence of broad absorption up to ca. 700 nm, complemented
by uorescence emission reaching the NIR region of the
spectrum (em = 679 nm, F = 0.04). The nanographene
showed three reversible redox events at Eox1 = 0.62 V, Ered1 =
1.45 V, and Ered2 = 1.66 V (vs Fc/Fc+). The solid-state
structure of 14.3 revealed deviations of the fused core from
planarity, caused by steric overcrowding in the cove regions.
Using an analogous structural paradigm and an on-surface
synthetic strategy,88 Kawai et al. developed in 2015 a synthesis
of boron-doped graphene nanoribbons.89 In the initial
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Scheme 15. Synthesis of 6a,12a-Diaza-6a1,12a1diboracoronene Derivativesa
Scheme 17. Synthesis of BN-Doped Hexa-perihexabenzocoronenea
Reagents and conditions: (a)93 Ar atm, 6 h, 550 C.
cyclodehydrogenation of 18.1 proceeded smoothly to 18.3

(Scheme 18). 18.3 showed good solubility in organic solvents
and had excellent thermal stability in the solid state. The UV
vis spectrum of 18.3 contained absorptions characteristic of the
basic HBC structure, with two additional weak bands at 450
and 490 nm. 18.3 exhibited a strong emission band at 545 nm,
which was quenched by gradual addition of triuoroacetic acid.
Heteroleptic ruthenium and palladium complexes of 18.1
and 18.3 were obtained in reactions with appropriate bipyridyl
or allyl complexes (Scheme 18).95 Compound 18.4 turned out
to be unstable in solution or after irradiation with visible light.
In 18.7, Pd(II) coordination caused a red-shift in the lowenergy absorptions, a decrease in the intensity of the n*
absorptions, and a quenching of the uorescence emission.
Each of the RuII compounds 18.6a and 18.6b possessed two
discernible 1MLCT bands covering the entire visible range, and
was therefore classied as a black absorber. The lower energy
band (max = 615 nm) showed an associated 3MLCT emission
(max = 880 nm), due to the unprecedented electron
delocalization and acceptor properties of the rigid aromatic
ligand 18.3. Both RuII complexes are near-IR emitters with
unusually protracted emission lifetimes of 320 ns at 77 K.
Cyclic voltammograms of 18.6a showed two sequential oneelectron reductions associated with the 18.3 ligand, and two
observable oxidation processes. These reduction potentials
were anodically shifted when compared to the bpy-based
reduction potentials, conrming the extensive delocalization
and the presence of low-lying *-orbitals in the 18.3 ligand.
Temperature- and concentration-dependent NMR studies on
18.7 and 18.6a suggested that extensive aggregation was
occurring in solution.
A partially coupled N-heterosuperbenzene, 18.2, was
obtained alongside 18.3 as a product of oxidative cyclodehydrogenation performed with iron(III) chloride instead of
AlCl3/CuCl2 used in the earlier report (Scheme 18).96
a
Reagents and conditions: (a)90 Pd(dba)3, P(o-Tol)3, 1,2,4-trichlorobenzene, 12 h, 170 C; (b) (1) n-BuLi, o-dichlorobenzene, 2 h, 0 C,
(2) BBr3, 24 h, 180 C.
cleaved. The possibility of sequential replacement of substituents, yielding systems 16.35, was envisaged as a means of
ne-tuning the electronic properties of these BN coronenes.
In 2015, Bettinger and co-workers described the synthesis of
a hexa-peri-hexabenzocoronene with a central borazine core
17.2 (Scheme 17).93 The desired compound was prepared by
thermolyzing N,N,N-tris(2-biphenylyl)borazine 17.1 at 550
C for 6 h. After sublimation, 17.2 was isolated as a poorly
soluble yellow powder. The solid-state structure of 17.2 is
isotypic with that of the parent hexa-peri-hexabenzocoronene,
as shown by a powder X-ray diraction analysis. Scanning
tunneling microscopy enabled direct observation of 17.2 on the
Au(111) surface, revealing preferential alignment of the
symmetry axes of the molecule relative to the substrate.
2.4. peri-Condensed Coronenes
The rst example of a coronene peri-fused to a heterocyclic ring

was provided by tetra-peri-(tert-butyl-benzo)-di-peri-(pyrimidino)-coronene 18.3, which was reported in 2002 by Draper and
co-workers.94 18.3, the rst member of the N-heterosuperbenzene family, was synthesized in a two-step procedure,
beginning with the DielsAlder cycloaddition between
tetraphenylcyclopentadienone and di(pyrimidin-3,5-yl)ethyne.
This cycloaddition yielded the heteroaromatic hexaarylbenzene
18.1, containing two adjacent pyrimidine rings. Oxidative
Scheme 16. Synthetic Routes to BN-Embedded Coronene Analoguesa
Reagents and conditions: (a)91 dichlorophenylborane, Et3N, o-dichlorobenzene, N2 atm, 12 h, 180 C; (b)92 dichlorophenylborane, Et3N, odichlorobenzene, Ar atm, 24 h, reux; (c) chloroform, 1 week; (d) chloroform, 2 weeks.
a
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Scheme 18. Synthetic Routes to N-Heterosuperbenzenes and Their Complexesa
Reagents and conditions: (a)96 FeCl3/CH3NO2, DCM, Ar atm, rt, 30 min; (b)94 AlCl3, CuCl2, CS2, rt, 72 h; (c)95 (1) [Ru(bpy)2Cl2]2H2O,
AgBF4, acetone, reux, 1.5 h, (2) n-BuOH, acetone, (3) 18.1, DCM, n-BuOH, reux, 72 h; (d)96 (1) [Ru(bpy)2Cl2]2H2O, diethylene glycol ethyl
ether, sonication, 10 min, (2) Ar purging, 30 min, (3) 20 h, 127 C; (e)95 (1) [Ru(bpy)2Cl2]2H2O or [Ru(bpy-d8)2Cl2]2H2O, diethylene glycol
ethyl ether, sonication, 10 min, (2) Ar purging, 30 min, (3) 20 h, 127 C; (f) (1) bis(chloro-3-allyl palladium), MeCN, DCM, AgNO3, 6 h, rt, (2)
ltration over Celite, (3) 16.3 in toluene, 12 h, rt.
Chart 6. Methoxy-Functionalized97 and Terpyridine-Fused98 Coronene Derivatives
Compound 18.2 did not undergo further oxidative coupling in

the presence of either reagent, indicating that it was
thermodynamically stable and that it formed independently of
18.3. In analogy to 18.3, 18.2 produced a complex with RuII,
18.5 (Scheme 18). 18.2 exhibited photophysical properties
consistent with a less conjugated /* framework, including an
increase in the energy of the LUMO, and a blue-shift of the

solvent-dependent uorescence (em = 474 nm, F = 0.55,
toluene), as compared to 18.3. Complex 18.5 absorbed
throughout the visible region, exhibiting a slightly blue-shifted
3
MLCT emission (868 nm, CH3CN) in comparison with
18.6a. Electrochemical analyses permitted further elucidation of
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Scheme 19. Synthesis of Chevron-Shaped Graphene Nanoribbons Doped Nitrogen Atomsa
Reagents and conditions: (a)17 250 C; (b) 440 C.
pyridyl rings in the Scholl reaction. The absorption and

emission properties of the RuII bis-terpy complex of ligand
C6.5 were comparable to those of [Ru(terpy)2]2+. The new
complex was nonemissive at room temperature but emitted at
77 K with excited-state lifetimes of 12 s.
In 2013, Bronner, Hecht, Tegeder et al. proposed a synthesis
of chevron-shaped graphene nanoribbons consisting of fused 2aza- or 2,5-diaza-HBC subunits (19.3a,b, Scheme 19).17 These
compounds were obtained from triphenylene monomers
19.1a,b, by means of an on-surface coupling strategy developed
earlier for the analogous all-carbon nanoribbons.88 Adsorption
of several layers of monomers (19.1) on Au(111) and heating
at 250 C led to desorption of the second and higher layers as
well as halogen dissociation and coupling of the resulting
activated biradical monomers, yielding a sterically crowded and
hence twisted polyphenylene 19.2. In a second heating step at
440 C, these polymers underwent a subsequent cyclodehydrogenation reaction to yield the completely fused
nanoribbon 19.3. Using angle-resolved high-resolution electron
energy loss spectroscopy (HREELS) in combination with
photoelectron spectroscopy, the researchers showed that the
band gap is linearly shifted relative to the electronic structure of
the environment of the graphene nanoribbons but remains
almost unchanged in magnitude, as expected for pyridine-like
the intermolecular interactions of 18.6a and 18.5. These results

and the concentration- and temperature-dependent NMR
spectra of 18.5 conrmed the complex to be nonaggregating,
a direct result of the two uncyclized and rotatable phenyl rings
in 18.2.
Methoxy-substituted N-heterosuperbenzenes containing one
(C6.3) or two pyrimidine rings (C6.1 and C6.2, Chart 6) were
obtained similarly to 18.3.97 In the solid state, C6.1 and C6.3
showed a slight distortion of the aromatic core and two distinct
types of columnar stacking. The absorption and emission
spectra of C6.1, C6.2, C6.3, and C6.4 were comparable with
those of other N-heterosuperbenzenes.9496 For all compounds, broadening of emissions and solvatochromic shifts
were observed in methanol, possibly associated with the
formation of an intramolecular charge-transfer (ICT) excited
state, which was stabilized by polar solvents. Cyclic voltammograms showed that each of the completely coupled compounds
C6.1, C6.2, and C6.3 possessed a single irreversible oxidation
wave under positive potential and one reversible reduction.
Terpyridine-containing derivatives C6.5 and C6.6 were
prepared by Draper et al. in 2012, by employing Scholl
reaction conditions similar to those used for the synthesis of
18.3.98 Compounds C6.5 and C6.6 were obtained, respectively,
in 34% and 5% yields, showing the lower reactivity of the
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Scheme 20. Synthesis of S-Doped Hexabenzocoronenesa
Reagents and conditions: (a)101 FeCl3/CH3NO2, DCM, rt, 5 h.
nitrogen at the edges of armchair graphene nanoribbons. In

2014, using a similar procedure, Mullen, Fasel, and co-workers
prepared another example of a nitrogen-doped graphene
nanoribbon consisting of 1,3,4,6-tetraaza-HBC subunits
(19.5) as well as hybrid nanoribbons combining undoped
and nitrogen-doped segments (19.6).99 The heterostructure of
the nanoribbon was conrmed by scanning probe methods, and
it was shown to behave similarly to traditional pn junctions. A
band shift of 0.5 eV was determined for this material as well as
an electric eld of 2 108 V m1 at the heterojunction. In the
same year, Sinitskii et al. proposed a bulk synthesis of the 1,3diaza-HBC nanoribbon 19.4, obtained as a highly insoluble
powder in a sequence of Yamamoto and Scholl coupling
reactions.100 However, the unsymmetrical structure of the
precursor resulted in a nonuniform distribution of N-doping
sites in 19.4.
Oxidative cyclodehydrogenation of the thienyl precursor
20.1, reported by the Draper group, yielded the thieno-fused
coronene derivative 20.2 and its dimer 20.3 (Scheme 20).101 It
was presumed that the intramolecular couplings involving the
thiophene rings occurred prior to the intermolecular coupling
of the 20.3 dimer. Photochemical and electrochemical
properties of the monomer and dimer were similar to those
reported in the literature for the all-carbon analogues of
hexaalkyl-substituted coronenes. Nevertheless, the dimeric
structure exhibited dual luminescence that varied with
concentration. This behavior was explained in terms of a
concentration-dependent conformational change involving the
orientation of the two HBC-like subunits in 20.3, likely
associated with the formation of excited-state aggregates.
In 2015, a new class of peri-thiophene-fused coronenoids was
developed by Mullen and co-workers.102 Triply annulated HBC
derivatives 21.2ac, accompanied by traces of the bisannulated 21.3a,c, were obtained by exhaustive thiolation of
perchlorinated HBC (21.1, Scheme 21). The bay-selective
sulfur annulation probably results from the minimization of
strain in the aromatic core, incurred upon the initial thiolate
substitution (for a related example, cf., Scheme 54, section 3.2).
The densely functionalized -electron system in 21.2a is
characterized by an optical bandgap that is reduced by ca. 0.5
eV relative to the unsubstituted HBC. In 2015, Zheng, Tan et
al. employed 21.2a as the hole-transport material in perovskite
solar cells, yielding eciencies of up to 12.8% in pristine form,
and up to 14.0% when doped with graphene sheets.103
Scheme 21. Synthesis of Thiophene-Fused p-HBC

Derivativesa
Reagents and conditions: (a)102 sodium thiophenolate, dry 1,3dimethyl-2-imidazolidinone, 0 C to rt in 5 h.
employ oxidative annulations of heteroaromatic substituents

attached to PAHs (in particular perylene) or direct assembly of
a hetero ring on the periphery of a PAH. The latter method was
employed in the early synthesis of the quinoxalino-fused
coronene 22.3 described in 1952 by Zinke and co-workers.54
Compound 22.3 was obtained from coronene-1,2-dione and
ortho-phenylenediamine in the presence of nitrobenzene and
glacial acetic acid. The same approach was used in 2008 by
Mullen and co-workers to obtain a triply quinoxalino-fused
coronene derivative, 22.6.104 In 2009, Liu, Sanguinet et al.
employed the same strategy to obtain the coronenetetrathiafulvalene hybrid 22.7, characterized by extended conjugation.105 This triply TTF-fused compound was obtained
via direct condensation of coronene-1,2,5,6,9,10-hexaone
(22.5) with 5,6-diamino-2-[4,5-bis(hexylthio)-1,3-dithio-2ylidene]benzo[d]1,3-dithiole (Scheme 22). Compound 22.7
possessed strong ICT absorption in the visible part of optical
spectrum (max = 580 nm) and yielded a NIR-absorbing
cationic species upon oxidation with (NO)[SbF6], which was
interpreted as the [22.7]3+ trication. Quinoxaline condensations
were also used recently by Xiao et al. for the synthesis of ladder-
2.5. ortho-Condensed Coronenoids
2.5.1. Coronenoids Fused to Azaheterocycles. Several

strategies are available for the synthesis of coronenoids
containing ortho-fused heterocyclic rings. Typical approaches
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Scheme 22. Synthetic Routes to Quinoxaline Derivatives of Coronenea
Reagents and conditions: (a)54 (1) nitrobenzene, glacial AcOH, (2) Na2Cr2O7, glacial AcOH; (b) nitrobenzene, glacial AcOH, ophenylenediamine; (c)104 (1) BBr3, DCM, overnight, rt, (2) HNO3, 1 min, rt; (d) o-phenylenediamine; (e)105 DMF/AcOH (7/1), 160 C,
microwave irradiation.
Scheme 23. Synthesis of Pyrido-Annulated Coronenesa
Reagents and conditions: (a)106 pyridin-4-ylboronic acid, Pd(PPh3)4, THF, 2M K2CO3, 4 h, reux; (b) h, DCM, 5 h, rt; (c) pyridin-4-ylboronic
acid, Pd(PPh3)4, THF, 2M K2CO3, 24 h, reux; (d) iodomethane, MeCN, 30 h, reux; (e)107 h (halogen lamp, 500 W), ethyl acetate, 10 h; (f)
TFA, chloroform, overnight, rt.
like oligomers 22.8 and 22.9, comprising respectively dibenzo[a,j]coronene and naphtho[1,2,3,4-ghi]perylene subunits.
A bis-pyrido-fused coronene 23.3 was prepared by Wang et

al. in 2010 (Scheme 23).106 Its synthesis, which applied the
W
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Scheme 24. Synthesis of Ladder-Type Perylene Derivativesa
Reagents and conditions:108 (a) I2, toluene, h, O2, rt, 3 h; (b) 4-methylbenzenesulfonic acid, 110 C, 3 h; (c) dodecylamine, imidazole, 200 C, 4
h.
Scheme 25. Synthesis of Thiophene-Fused Coronene Derivativesa
a
Reagents and conditions: (a)110 cat. I2, h, DCM, 2 h, rt; (b)111 FeCl3/CH3NO2, DCM, 20 min, rt, Ar atm; (c)112 FeCl3/CH3NO2, DCM, 30 min,
rt, Ar atm.
noncyclized precursor 23.5. The t-butyl-protected compound

23.6 showed strong green uorescence. The emission of the
water-soluble derivative 23.7 was weaker and had a yellow-toorange color.
Coronene derivatives containing two ortho-fused carbazole
units were reported in 2011 by Xiao et al. (Scheme 24, for
structurally related ladder PDI chromophores C11.67, see
section 3.3).108 The target structures 24.4 and 24.6, containing
the PDI motif, were obtained from isomeric bis-carbazolyl
perylene precursors (e.g., 24.1 for 24.4) by means of a double
photocyclization reaction, followed by conversion of the
tetraester into the diimide. Compounds 24.4 and 24.6 have
good solubility in common solvents and showed enhanced
third-order nonlinear properties in comparison with the parent
nonfused PDI.
substituent annulation strategy to the PDI precursor 23.1,

could be performed as a sequence consisting of Suzuki crosscoupling and Mallory photocyclization, or in a one-pot fashion,
by extending the reaction time of the Suzuki coupling step. The
dicationic derivative 23.4, obtained by quaternization with
methyl iodide, was characterized by a drastic reduction in the
uorescence intensity relative to 23.3. In 2011, Hirsch et al.
reported on the synthesis of water-soluble triazole-fused
coronenes.107 Hexaester 23.6 was obtained by UV irradiation
of the bay-functionalized precursor 23.5. The double
cyclization reaction was signicantly slower than the analogous
single cyclization leading to the triazole-fused benzoperylenes
C11.3a4a (section 3.3). Deprotection with triuoroacetic
acid led to the free hexacarboxylate 23.7. 23.6 and 23.7 had
absorption spectra with sharper bands and higher extinction
coecients, and exhibited stronger uorescence than the
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Chart 7. Dithienocoronene Diimide-Based Conjugated Polymers113115
2.5.2. Thieno-Fused Coronenoids. Coroneno[1,2-b:7,8b]dithiophene 25.3a was prepared by Ko et al. in 2011

(Scheme 25).109 Its tetraester analogue 25.2 was reported in
2014 by Xiao et al., who similarly used the Mallory
photocyclization in the nal step.110 Estimated HOMO and
LUMO levels in 25.2 were about 0.4 eV higher than in the
diimide, indicating that the tetraester was less electron decient
and easier to be oxidized. 25.3a was subsequently functionalized with oligothienyl substituents to provide derivatives
25.3b,c, with bathochromically shifted absorptions. On the
basis of these coronene derivatives, bulk-heterojunction organic
solar cells were prepared, yielding power conversion eciencies
of up to 1.42%. Thiophene-annulated core-extended rylene
diimides, terrylene 25.6 and quaterrylene 25.7, were obtained
by Negri, Wang,111 et al. in 2012. Thiophene units were
introduced regiospecically using Stille cross-coupling of a
brominated terrylene with 2-(tributylstannyl)thiophene, to
yield the thienyl-substituted precursor 25.5. For the quaterrylene derivative, thienyl regioisomers could be easily separated
by chromatography. The nal annulations were performed
under typical Scholl reaction conditions using iron(III) chloride
(Scheme 25). These thiophene-annulated rylenes were poorly
soluble in common organic solvents and exhibited hypsochromic shifts relative to the parent perylenediimide. Their
uorescence was characterized by small Stokes shifts (812
nm) and high uorescence quantum yields (0.56 and 0.14 for
25.6 and 25.7, respectively).
A range of dithienocoronene-containing polymers were
developed by several research groups. Donoracceptor (D
A) systems reported in 2012 by Usta, Facchetti,113 et al.
consisted of dithienocoronene diimide acceptor units linked
with thiophene, bithiophene, or 3,3-dialkoxybithiophene donor
moieties (Chart 7). Polymers were obtained from dibromodithienocoronenediimide 25.4, which was subjected to the Stille
coupling reaction with an appropriate donor derivative. The
near-linear linkage geometry of dithienocoronenediimide is
crucial for achieving a high degree of regioregularity in the
polymeric backbone, which is of importance in organic thinlm transistor (OTFT) devices. Top-gate bottom-contact
TFTs were produced by spin-coating solutions of C6.1a and
C7.1c. Ambipolar behavior was observed in ambient, with
electron and hole mobilities of up to 0.30 and 0.04 cm2 V1 s1,
respectively. A conjugated copolymer C7.2 combining planar

dithienocoronene diimide acceptor units with strongly donating
porphyrin moieties was prepared in 2012 by Duan, Zhan, et
al.114 The polymer was synthesized through the Sonogashira
coupling reaction of an appropriate Zn diethynylporphyrin with
the dibromodithienocoronenediimide 25.4. Polymer C7.2
exhibited a low bandgap (1.44 eV) and good thermal stability
(decomposition temperature of 323 C). It also possessed
strong absorption in the 300900 nm range with a molar
extinction coecient per repeat unit of 1.05 105 M1 cm1 in
the CHCl3 solution. As compared to a perylenediimide
porphyrin polymer,116 C7.2 exhibited up-shifted HOMO and
LUMO levels and blue-shifted absorption, as a consequence of
its weaker electron-withdrawing ability. High two-photon
absorption (TPA) cross sections were measured for C7.2,
with a maximum of 7809 GM per repeat unit at 1520 nm.
Zhan115 et al. reported the synthesis of a series of n-type
semiconducting polymers C7.3ad by Pd-catalyzed Stille
coupling polymerization. Those compounds were based on
the dithienocoronenediimide core linked with oligothiophenes
of varying lengths (m = 03 units, Chart 7). Compound C7.3d
was insoluble in common organic solvents. The soluble
polymers C7.3ac exhibited good thermal stability, with
decomposition temperatures of 340390 C, and showed
progressively red-shifted absorption spectra with increasing m
number. The optical band gap was estimated as 1.71.9 eV and
was found to decrease with increasing m. Interestingly, the
estimated HOMO values (6.0 to 5.7 eV) were also
increasing with increasing m, whereas the LUMO values (ca.
3.5 eV) remained virtually constant. Solution-processable
BHJ all-polymer solar cells were fabricated using compounds
C7.3ac as acceptors and a polythiophene derivative
PT5TPA117 as the donor. Measured power conversion
eciencies (up to 0.84%) were also observed to increase with
the linker length.
Tri(benzothiopheno)hexa-peri-hexabenzocoronene 26.2, the
rst synthesized example of large PAHs fused with electron-rich
thiophene rings, was reported in 2007 by Mullen and coworkers.118 Compound 26.2 was obtained by means of a 6-fold
intramolecular oxidative cyclodehydrogenation of the oligoaryl
precursor 26.1 (Scheme 26). Compound 26.2, which may be
described as a triply benzothiophene-fused HBC, is poorly
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Scheme 26. Triply Thiophene-Fused Coronenoidsa
triphenylene derivative. 26.4 possesses a planar conformation in

the solid state, due to the smaller size of thiophene ring, which
eliminates steric congestion present in other similarly fused
coronenes reported in the same work. 26.4 also exhibited lower
HOMO energy levels, in line with the electron-donating
properties of thiophene.
Trithieno hexa-cata-hexabenzocoronene (c-HBC) analogues
27.3ac were synthesized in 2014 by Wei and co-workers.120
These authors used a covalent self-sorting assemble (CSA)
strategy, which was devised as a two-step reaction sequence
(Scheme 27). In the rst step, sym-tribenzylbenzenes 27.2ac
were obtained through the Suzuki cross coupling of 1,3,5tri(bromomethyl)-benzene with 3,4-dialkoxyphenylboronic
acids. In the nal, self-sorting step, c-HBC derivatives were
obtained in a tandem FriedelCrafts/oxidative coupling
reaction between 27.2ac and aryl aldehydes. The use of
thiophene-3-carbaldehyde yielded the triply thieno-fused
coronenes 27.3ac.
Dibenzotetrathienocoronenes 27.5ag, rst described in
2010 by Nuckolls and co-workers,121,122 are structurally and
synthetically related to contorted hexabenzocoronenes (cHBCs).59 A variety of tetrasubstituted derivatives 27.5ag were
obtained by photocyclization of the pentacene precursors
27.4ag. The latter compounds were prepared using Suzuki
cross-coupling. In the solid state, 27.5ag adopted either the
up-down or buttery conformation, depending on the
substitution pattern and crystallization conditions. In particular,
cocrystallization with small (TCNQ) and large electron
acceptors (C60) stabilized the up-down or buttery
conformations, respectively.121 27.5c forms columnar stacks
capable of hole transport in the solid state. Upon annealing,
spuncast layers of 27.5c became organized into reticulated
Reagents and conditions: (a)118 FeCl3, CH3NO2, DCM, 40 min, rt;

(b)112 FeCl3, DCM, 30 min, rt.
soluble in common organic solvents, and its absorption and

uorescence spectra exhibit a blue shift of 10 and 30 nm,
respectively, as compared to HBC itself. 26.2 was successfully
processed into thin layers using pulsed laser deposition
(PLD).119 A smaller trithiophene system, coroneno[1,2-b:5,6b:10,9-b]trithiophene 26.4, was obtained by Wang et al. in
2009.112 The structure of the trithienyl precursor 26.3 was
dictated by the availability of the unsymmetrically brominated
Scheme 27. Synthetic Pathways to Thienocoronene Derivativesa
Reagents and conditions: (a)120 (1) Na2CO3, acetone/water (1/1), Ar atm, 10 mol % PdCl2, 1,3,5-tris(bromomethyl)benzene, 0 C, (2) 12 h, rt,
(3) 3 days, 3738 C; (b) (1) Ac2O, DCM, FeCl3, CH3NO2, Ar atm, 1 h, rt, (2) 27.2, DCM, FeCl3, CH3NO2, Ar atm, 1 h, rt; (c)121 I2, h,
propylene oxide, benzene, N2 atm, 4 h, rt.
a
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Scheme 28. Quinoxaline Assemblies Based on Tetrabenzo[bc,ef,hi,uv]ovalene-1,2-dionea
Reagents and conditions:127 (a) 3,3-diaminobenzidine tetrahydrochloride, AcOH, reux, 3 d; (b) o-phenylenediamine dihydrochloride, AcOH,
reux, 3 d; (c) AcOH, 1,2-diamino-4,5-dicyanobenzene, reux, 6 h; (d) 5,6-diamino-1,10-phenanthroline, pyridine, reux, 16 h; (e) 1,2,4,5benzenetetraamine tetrahydrochloride, AcOH, reux, 8 d; (f) DMF, cis-bis(2,2-bipyridine)ruthenium(II) chloride, reux, 3 days; precipitation from
aqueous NH4PF6; (g) urea, CuCl2, quinoline, 220 C, 16 h.
28.7. The presence of t-butyl groups in the bay regions of the

ovalene block apparently led to out-of-plane distortions of the
aromatic surface, which translated into increased solubility of
the products, that could be puried chromatographically and
produced well-resolved 1H NMR spectra. 28.6 was found to be
a quadrupolar (donoracceptordonor) system, with the
LUMO level partially localized in the central part of the
molecule. The quadrupolar character of 28.6 led to a marked
solvatochromic eect in the uorescence emission spectra
(maxem = 658 nm in cyclohexane and 740 nm in THF/MeCN),
indicating the presence of a polar excited state. In contrast, the
absorption spectra of 28.6 showed very weak solvent
dependence. With 224 atoms in the aromatic core, 28.8 is
apparently the largest monodisperse PHA system reported to
date. It showed a considerably red-shifted absorption spectrum,
with an optical bandgap of 1.34 eV (869 nm).
layers, which were found to provide excellent bulk heterojunctions for use in photovoltaics upon doping with C60.122 In
subsequent work, a supramolecular complex was found to form
in lm blends containing 27.5c and phenyl-C70-butyric acid
methyl ester (PC70BM).123 This complex formed the supramolecular heterojunction in the rst fully solution-processed
photovoltaic device with ball-and-socket motif, showing a solar
eciency of 2.7%.
Structurally related hexathienocoronenes (HTCs) 27.7a,b
and 27.8ac were reported in 2012 by Mullen and coworkers.124 These compounds, obtained using dehydrogenative
photocyclizations, revealed remarkable self-assembly behavior
in solution, in the solid state, and at the solutionsubstrate
interface. 27.8c forms a columnar mesophase over a wide
temperature range close to room temperature, much lower than
measured for the structurally related hexadodecylhexabenzocoronene. Hexathienocoronene 27.8d, reported in 2013 by
Mullen, Chen, and co-workers,125 had a substitution pattern
containing two alkyl chains and two oligoether groups,
designed to provide a gemini-type amphiphilic structure of
the type described earlier by Aida, Fukushima, et al.126 To
achieve amphiphilic functionalization of the HTC core, the
authors introduced two kinds of thiophene segments in a
stepwise manner (as pinacol boronic esters), and completed the
fused aromatic framework in 27.8d using a dehydrogenative
photocyclization. The choice of solution-processing conditions
allowed the tuning of supramolecular structures from bers to
helices and tubes. This property was probably associated with
the slightly twisted skeleton of 27.8d and its amphiphilicity. In
particular, self-assembly at the liquidsolid interface led to the
formation of large domains of defect-free monolayers. An STM
study of these monolayers showed a peculiar packing pattern, in
which pairs of molecules were adsorbed very close to each
other and arranged in the p2 plane group. 27.8d formed a
stable radical cation upon oxidation with (NO)[BF4], and
yielded a strong photocurrent in PCBM blends.
In 2007, Mullen et al. reported the synthesis of substituted
tetrabenzo[bc,ef,hi,uv]ovalene-1,2-dione 28.1 and demonstrated
its use as a building block for the synthesis of a variety of orthofused quinoxaline systems 28.26 (Scheme 28).127 The
dicyano compound 28.4 was subsequently converted into the
copper(II) phthalocyanine 28.8, whereas the phenanthroline
derivative 28.5 was transformed into the ruthenium complex
3. PERYLENOIDS
The current interest in perylene derivatives is motivated by
their importance for materials science, notably in the area of
organic electronics. Recent advances in the eld have been
reviewed by several authors (see section 1.2 for references).
The perylene chromophore can be modied in a number of
ways, including extension into rylene ribbons, bay-region
substitution and fusion, and terminal substitution and fusion.
Perylene mono- (PMIs) and diimides (PDIs) are among the
most studied derivatives because of their easy accessibility and
commercial importance. As explained in section 1.2, PMI and
PDI systems, containing no additional heteroannulated motif,
will not be covered here. The remaining material is divided into
ve sections (Chart 8). Heteraperylenoids, discussed in section
3.1, contain at least one heteroatom in a fully conjugated
perylene substructure. Perylenes containing ve- and sixmembered rings fused to the bay region ([ghi]-fusion) are
covered, respectively, in sections 3.2 and 3.3. peri-Fusion at the
perylene terminus ([cd]-fusion) is discussed in section 3.4,
whereas ortho-heteroannulated systems ([a]- and [b]-fused) are
presented in section 3.5. In each section, perylene denes the
minimum required extent of fusion, and we include any larger
system not containing the coronene motif.
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that, after the rst Stille coupling between 29.5 and 29.6, an
intramolecular Heck-type cyclization eectively competed with
the second intermolecular coupling under typical reaction
conditions.
The rst synthesis of a monoazaperylene, 1-azaperylene
29.15, was reported in 2010 by Gryko et al.131 29.15 was
obtained in an anionic radical coupling reaction132 from each of
the two isomeric naphthyl isoquinoline precursors 29.14 and
29.16. 1-Azaperylene could be directly functionalized with
either the OH or the CN group, yielding, respectively, the
substituted derivatives 29.17 and 29.18. 29.15 and 29.18 are
strongly emitting uorophores (F > 80% in cyclohexane). The
emission from 29.17 was weaker (17% in cyclohexane), but the
chromophore itself showed a considerable bathochromic shift
of 75 nm for the lowest energy absorption. While an ESIPT
process was envisaged for 29.15, no conclusive experimental
evidence could be oered, apparently because of the
unfavorable overlap of emissions for the keto and phenol
tautomers.
3a1-Azoniaperylene bromide 29.21, an extended cyclo[3.3.3]azine133 analogue, was reported in 1991 by Fourmigue,
Eggert, and Bechgaard.134 The key precursor, quinolizinium
bromide 29.20, was obtained by acid-catalyzed cyclization of
the pyridine derivative 29.19. 29.20 was subsequently cyclized
with 2,3-dihydroxy-1,4-dioxane, a masked glyoxal equivalent, to
produce the azoniaperylene 29.21 in 55% yield. 29.21 showed
charge delocalization and magnetic properties consistent with
its formulation as a combination of weakly interacting
naphthalene and quinolizinium units. It could be reversibly
reduced (E1/2 = 1.08 V vs SCE) to a neutral radical
isoelectronic with the perylene radical anion.
Chart 8. Classication of Perylenoids Used in This Sectiona
a
indicated.
3.1. Heteraperylenoids
3.1.1. Monoheteraperylenoids. Early examples of perylenoid structures containing a single embedded heteroatom
were provided in 1946 by Schonberg et al.128 and in 1957 by
El-Shafei and Ismail,129 who synthesized the fused xanthene
(29.3) and thioxanthene (29.4) derivatives in light-induced
oxidative cyclizations of the respective ethylenes 29.12
(Scheme 29). Two isomeric monoazaperylene derivatives
29.7 and 29.8 were obtained unselectively as byproducts in
the synthesis of the sterically congested 1,8-diarylnaphthalene
29.9, as reported in 2003 by Wolf and Mei.130 It was found
Scheme 29. Monoheteraperylenesa
Reagents and conditions: (a)128,129 benzene, sunlight, 24 weeks; (b)130 Pd(PPh3)4, DMF, 100140 C, 518 h, up to 17% of 29.7 and 29.8;
(c)135 AlCl3 (3 equiv), S8 (1.5 equiv), NEt(i-Pr)2 (2.0 equiv), toluene, 80 C, 1218 h; (d)135 (1) PEt3, chlorobenzene, 0 C, (2) 120 C, 12 h;
(e)131 (1) K, toluene, (2) air; (f)131 Pd(OAc)2, PhI(OAc)2, n-BuOH; (g)131 Pd(OAc)2, CuCN, CuBr2; (h)134 HBr (48%), AcOH, reux, 3 h; (i)134
EtOH, NEt3, reux, 2 h.
a
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A perylenoid substructure with an embedded phosphorus

atom 29.13 was reported in 2011 by Hatakeyama, Nakamura,
et al. (Scheme 29).135 In the initial synthetic step, performed on
the dichloroarylphosphine 29.11, the fused framework was built
around the P atom in a phospha-FriedelCrafts reaction. The
resulting phosphine sulde 29.12 was subsequently oxidized to
the respective oxide or reduced to the free phosphine 29.13. In
all derivatives, the CP bonds retain a pyramidal geometry. In
solution, 29.13 shows a strong green uorescence, which
includes an excimer-type emission at 540 nm. The phosphine
center in 29.13 is capable of metal coordination, and a gold(I)
complex, (29.13)AuCl, was isolated and structurally characterized.
Vinylogous NMI and PDI derivatives 30.24, developed in
2015 by the Mullen group, contain the 3a1-azaperylene
substructure with a nitrogen atom at a peri-fusion point.136
The simplest system, 30.2, was obtained in a tandem
condensation between naphthalene monoanhydride and the
diacetylaniline 30.1. The analogous condensation leading to
30.4 was low-yielding (5%) and was replaced with a sequential
route. 30.2 was further modied by double olenation of the
enone moieties with malonodinitrile. 30.24 showed considerably red-shifted absorption spectra relative to the parent NMI
and PDI systems (max = 451, 630, and 700 nm, respectively).
30.4 displayed strong uorescence with a relatively small Stokes
shift ( = 26 nm, F = 0.45).
Scheme 31. Synthesis of Monoheteraperylenes Doped with a

Boron Atoma
Reagents and conditions: (a)137 1,1-azobis(cyclohexanecarbonitrile),

(Si(CH3)3)3SiH, dry toluene, 120 C, 17 h; (b) pyridine-d5; (c) h;
(d) NBS, chlorobenzene, 120 C, 16 h; (e) phenylboronic acid,
Pd(PPh3)4, 2 M Na2CO3, toluene, EtOH, 90 C, 8 h.
coupling leading to compound 31.5. Despite this stabilization,

31.2 shows sucient Lewis acidity to form adducts with
pyridine and its derivatives in solution (31.3). The BN Lewis
adducts exhibit unprecedented photodissociation behavior in
the excited state, reminiscent of the photogeneration of
carbenium ions from triarylmethane leuco dyes. Consequently,
these BN Lewis adducts exhibit dual uorescence emission
arising from the initial tetracoordinate BN adducts and the
photodissociated tricoordinate boranes.
3.1.2. Diheteraperylenoids. 1,12-Diazaperylene 32.2a was
obtained in 2001 by Mullen, Mews, and co-workers in a
potassium/air-induced anionic radical coupling of 1,1bisisoquinoline 32.1a (Scheme 32).132 Interestingly, the 1,12diazaperylene framework could also be formed in 32.4, by
subjecting the mixed ruthenium complex 32.3 to catalytic
dehydrogenation, as shown in 2002 by Tor and Glazer.138
32.2a was then used to investigate heterosupramolecular
structures consisting of the diazaperylene chromophore and
CdSe or CdSe/ZnS core/shell nanocrystals. The observed
binding ratio was between 3 and 20 dye molecules per
nanocrystal. Nanocrystal uorescence quenching was observed
upon dye complexation, even for core/shell particles containing
just a few monolayers of the high bandgap ZnS semiconductor.
32.2a, typically denoted dap in coordination chemistry work,
was subsequently explored as a highly -conjugated ligand for
transition metals. Complexes of the general structure [M(dap)3]n+ were prepared for a range of metal ions, including
RuII,139 OsII,139 NiII,140 and FeII.140 Heteroleptic complexes
could also be prepared for RuII with the bpy ligand, and the
complex [Ru(bpy)2(dap)]2+ was found to photocleave plasmid
DNA.139 For sterically encumbered dap derivatives (32.2bd,
R = Me, Et, i-Pr), pseudotetrahedral [Cu(dap)2]+ complexes
were reported by Holdt et al. in 2009,141 and their stability was
subsequently explored in the gas phase using ESI mass
spectrometry.142 Polynuclear CuI and AgI complexes containing
dap and bridging phosphane ligands, exhibiting extended stacking in the solid state, were synthesized by Scheer, Lescop,
et al.143
Scheme 30. Vinylogous NMI and PDI Derivativesa
Reagents and conditions:136 (a) Zn(OAc)2, base, 140180 C; (b)

AcOH, Ac2O, malononitrile, reux.
In 2014, Yamaguchi and co-workers described the synthesis

of 7b-borauorantheno[1,10,9-abcd]perylene 31.2, a planarized
trinaphthylborane with partially fused structure (Scheme
31).137 The fused framework of 31.2 was prepared in one
step from tris(8-bromo-1-naphthyl)borane 31.1, which was
treated with (Me3Si)3SiH in the presence of 1,1-azobis(cyclohexanecarbonitrile) (ABCN) as a radical initiator. This
reaction resulted in the formation of 31.2, isolated as a red solid
in 26% yield. The fused framework of 31.2, which has a
connectivity consistent with a rearrangement of one of the
naphthyl groups, apparently confers high chemical and thermal
stability on the system. For instance, the boron moiety in 31.2
remained intact during further functionalization reactions, for
example, bromination and further SuzukiMiyaura crossAC
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Scheme 32. 1,12- and 3,9-Diazaperylenoids and Related Systemsa
Reagents and conditions: (a)132,141 (1) 1,2-DME, potassium, rt, 12 h, (2) air; (b)138 Pd/C, ethylene glycolacetone 10:1, 1 h, 175190 C; (c)144
70% H2SO4, reux, 30 min; (d)145 (1) UV irradiation, benzene, 2 h, 10 C, (2) UV irradiation, DCM, 1 h, rt, ca. 10% (two steps).
a
Scheme 33. 2,8-Diazaperylenoids and Related Systemsa
Reagents and conditions: (a)157 Na2S, DMF, reux, 3 h; (b) 2-methoxyethanol, KOH, 125 C, 4 h; (c)158 (1) phenol, KOH, 230 C, 30 min, (2)
H2O, air, overnight; (d) (1) H2SO4, H2O, Na2Cr2O7, (2) NaOH, NaHSO3, (3) aerial oxidation.
The purple-red bisacridine 32.6, containing the 3,9diazaperylene motif, was prepared in 1980 by cyclodehydration
of the diaminoanthraquinone derivative 32.5.144 This strategy,
rst employed in 1945 by Cook and Waddington,146 was later
used by Gibson and co-workers,144 and more recently by Bock
et al., who additionally prepared the extended tetraaza
derivative 32.7.147 Related work by Tokita et al. showed that,
when a tertiary diamine analogous to 32.5 was subjected to

cyclization in AlCl3NaCl, the nonquinoidal product 32.8 was
obtained (for related pyrenoid systems, see Scheme 89, section
4.2).148 To date, the only known fully conjugated nonfused 3,9diazaperylene is 32.10, rst reported in 1983 by Tatke and
Seshadri.149,150 However, a range of bis-lactams of the general
structure 32.9 has been reported by several research
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Scheme 34. Synthesis of Periazapyrenoidsa
Reagents and conditions: (a)159 DCM, 44 h, rt; (b) Br2, pyridine, DCM, 4 days, 8 C; (c) 34.2, DCM, 4 days, rt; (d) h (solidex glass, mercury
medium-pressure lamp), DCM, 30 min, rt; (e) h (solidex glass, mercury medium-pressure lamp), toluene, 3.5 h, rt.
groups151155 (for a structurally related triaza system, see ref

156).
-Expanded terpyridine 32.12 was obtained in 2015 by Wang
et al. in a photochemically induced oxidative cyclodehydrogenation of the nonfused precursor 32.11.145 The triple
annulation occurred in a stepwise manner, starting in the
vicinity of the ortho-phenylene linker, and all intermediates
were isolated. 32.12 was uorescent (maxem = 533 nm) and
formed heteroleptic RuII complexes containing an additional
nonfused terpyridine ligand.
Diazaisoviolanthrone dyes, such as the 33.3 derivative
originally described in 1972 by Boa et al.,157 are the key
examples of 2,8-diazaperylene systems (Scheme 33). 33.3 was
obtained from the azabenzanthrone derivative 33.1, which was
coupled into the thioether derivative 33.2 and rearranged into
the product under basic conditions. Acid- or base-induced
binary condensations of 7H-dibenzo[de,h]quinolin-7-one 33.5,
investigated in 1984 by Iwashima, Ueda, et al., were found to
produce mixtures of diazaperylenoids 33.610, which were
separated chromatographically.158 The structures of these
complex systems were elucidated from their oxidation products,
UVvis, IR, and mass spectra. Compounds 33.810 were
converted into violanthrone derivatives 33.1113 upon
treatment with sodium dichromate in concentrated sulfuric
acid. These violanthrones could be reduced back to the starting
materials in the presence of zinc chloride and zinc dust.
34.5, a 2,3-azaperylene-containing system, was reported in
1988 by Polansky and co-workers (Scheme 34).159 The
cycloaddition reaction between dibenzo[f,pqr]tetraphene 34.1
and 4-phenyl-1,2,4-triazoline-3,5-dione 34.2 produced a
mixture of products, containing a small amount of 34.5. The
noncyclic product 34.3 could be converted into 34.5, for
example, by treatment with dibromine. UV irradiation of the
original reactant mixture or 34.5 itself yielded the -expanded
diazepinone 34.6.
The synthesis of 3,10-diaza-3,10-dihydroperylene 35.2 and
related systems was achieved by Maeda and co-workers in the
photochemically induced cyclization of the lucigenin-derived
9,9-biacridinylidene 35.1.160 This method was later applied to
the synthesis of other derivatives.161 A dierent approach was
employed in 2007 by Fukai and Kimura, who observed that the
reductive coupling of acridinone 35.3 yielded directly the fused
product 35.4.162 35.4 showed red uorescence, with an
emission maximum at 609 nm and a quantum yield of 0.23.
The prototypical 1,7-diazaperylenoid, 36.2, was rst reported
in 1951 by Braude and Fawcett, who performed a reductive
Scheme 35. 3,10-Diazaperylenoidsa
Reagents and conditions: (a)160 h, benzene, 30 C, 17 h; (b)162 Zn

dust, TiCl4, dioxane, reux, 48 h.
a
double ring closure in the dinitro precursor 36.1 (Scheme

36).163 An alternative route to 36.2, involving a double ring
contraction of the bisthiazepine 36.3, was proposed in 1958 by
Galt et al.164 In 1998, Kobayashi et al.165,166 synthesized a
related system, 36.6, as a secondary photoproduct in the
photochemical cyclization of the diimine 36.4. The mechanism
of the cyclization was shown to involve an excited-state
intramolecular proton transfer (ESIPT) step.
A -extended 1,7-diazaperylenoid, 36.8, was obtained in
1988 by Kitahara and Nishi in a thermally induced selfcondensation of the diester 36.7.167 The initial structural
uncertainty was resolved in 1996 by an X-ray structural analysis,
which conrmed the double enol structure of 36.8.168 In lms
obtained by vapor deposition, the pigment exhibited a violet
color, which changed to reddish-purple upon exposure to
certain organic solvents, such as acetone. A 1997 study by
Mizuguchi revealed the presence of two crystalline phases,
corresponding to the two colors.169 The color dierence was
found to originate from changes in relative intensities of
vibrationalelectronic transitions, caused by variations of the
molecular environment. In 2011, Gisslen and Scholz reported a
theoretical investigation of the optical properties of 36.8 based
on an exciton model.170 The study revealed that the charge
transfer between stack neighbors increases the second moment
of the optical response. This behavior resulted in a red shift of
the neutral excitation energy.
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Scheme 36. 1,7-Diaza- and 3a,9a-Diazoniaperylenesa
Reagents and conditions: (a)163 Na2S2O4, MeOH, 5% NaOH, reux, 1 h; (b)164 copper bronze, diethyl phthalate, reux, 5 min; (c)165
photochemical; (d)167 1-chloronaphthalene, reux, 5 min; (e)171 NH3 (20%), Zn powder, rt, 2 h; (f) 2-chloropyrimidine, K2CO3, DMF, reux, 2 h;
(g) Raney Ni, cyclohexene, DMF, 110 C, 1 h; (h)172 urea, DMF, reux, 2 h; (i)173 reux, Ar, 48 h; (j)174 HgO, AcOH, reux, 48 h.
reported by Clar et al.55 (6.23, section 2.1). A conceptually

related approach was used by Gryko et al. to develop expanded coumarins 37.5ae as precursors to -expanded
pentacenes (see also Scheme 6, section 2.1).67 A synthetic
route complementary to 37.2c, involving an acid-catalyzed
cyclization of a disulfoxide 37.6, followed by demethylation,
was reported in 2010 by Liu et al.186 The red dixanthene 37.2a
is a photochromic compound, easily undergoing photooxidation to the colorless endoperoxide 37.3a.177 Heating the
latter species above 120 C regenerates the starting 37.2a
quantitatively. Photocycloreversion of the 37.3a and 37.3c
endoperoxides was investigated by Brauer and Schmidt187 and
by Jesse and Comes.188 37.2c was employed as a red emitter in
OLED devices, yielding current eciencies of up to 4.4 cd
A1.186
In 2010, Nishihara et al. reported that the treatment of a
diacetylene anthraquinone derivative 37.7 with the strong
protic acid TFSIH results in the formation of a double pyrylium
salt 37.8, containing the 1,7-dioxaperylene substructure.189 The
protonation and rearrangement of 37.7 occurred in a stepwise
manner, producing an unusual optical spectrum containing a
broad NIR absorption (up to 2200 nm), described as an
intervalence charge-transfer band. A biradicaloid contribution,
corresponding to the bis(ammoniumyl) valence structure 37.8,
was determined on the basis of ESR and SQUID measurements. In cyclic voltammetry, 37.8 underwent two reversible
one-electron reductions (0.06 and 0.16 V vs Fc/Fc+), and
could be chemically reduced to the highly unstable neutral
species 37.9, which was characterized in the solid state.
The parent 1,7-diazaperylene, 36.12, was reported in 1990 by

Naumann and Langhals.171 Their synthesis involved an
ammonia-mediated double cyclization of the anthraquinone
diacetate 36.9. The resulting dihydroxy intermediate 36.10 was
dehydroxylated in two steps to yield the unsubstituted product
36.12. A similar condensation approach was employed in 1992
by Gorelik and co-workers, who reported several substituted
derivatives of 36.12.175 A dierent strategy was employed in
2014 by Baranov et al., who cyclized ethynyl-substituted
anthraquinones 36.13ab in the presence of urea, obtaining
diazaperylenes 36.14ab in moderate yields.172
A uniquely short synthesis of the 3a,9a-diazaperylenium
dication 36.16 was reported in 2002 by Sotiriou-Leventis,
Leventis, et al.174 The hydrogenated p-phenylenediamine
precursor 36.15, which is extremely easily oxidizable, was rst
obtained by a one-step quadruple cyclization of p-phenylenediamine with 1-bromo-3-chloropropane.173 Dehydrogenation of
36.15 using mercury(II) oxide led to the formation of the
dication 36.16 and the monocation 36.17 in an approximately
1:3 molar ratio. 36.16 is a rare instance of a perylenoid
internally doped with nitrogen (an earlier example of a 6b,12bdiaza system 33.14 was reported in 1961 by Ziegler et al.176).
Benzo[1,2,3-kl:4,5,6-kl]dixanthene 37.2a177 and its analogues containing varying patterns of heteroatoms (37.2be)
and substituents,148,177184 as well as additional fused rings,185
were prepared from disubstituted anthraquinones 37.1ae,
following the strategy used for the synthesis of 32.6 (Scheme
37, for related earlier work, see ref 146 and references therein).
Related systems containing additional fused benzene rings were
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Scheme 37. O- and S-Containing 3,9- and 1,7-Diheteraperylenoidsa
Reagents and conditions: (a)148,177 AlCl3NaCl, hydroquinone 150180 C, 40%; (b) h, O2; (c) h or heat; (d)67 K2CO3, DMSO, 100 C;
(e)186 (1) TFA, (2) pyridine, no yield given; (f)189 TFSIH, DCM, rt, 3 min; (g) Li[TCNQ], MeCN/DCM, rt, 2 h.
Scheme 38. O- and S-Containing 3,10-Diheteraperylenoidsa
Reagents and conditions: (a)190 ZnCl2NaCl, rt to 300 C, 20 + 3 min; (b)191 benzene, N2 atm, Hg lamp, 64 h; (c)194 photolysis; (d)196 ultraviolet
irradiation, = 390 nm; (e)195 CHCl3, air, Xe lamp.
a
Compound 38.2, an early example of an extended 3,10dioxaperylenoid, was reported in 1964 by Lang and Zander
(Scheme 38).190 This ring system was obtained in one step
from the chrysene derivative 38.1, which was subjected to a
high-temperature acid-catalyzed condensation. In 1965, Schonberg and Junghans observed that photocyclizations of
bisxanthylenes 38.3ac produced good yields of the respective

benzodixanthenes (helixanthenes) 38.4ac.191 The photophysics of this reaction were subsequently investigated.192,193
38.4c was also found to form in the photolysis of the bisxanthogenate 38.5.194 The regioselectivity of bisxanthylene
photocyclization was explored in 2011 by Song and co-workers
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Scheme 39. Synthesis of a Doubly Boron-Bridged Dibenzo[g,p]chrysenea
Reagents and conditions: (a)198 (1) n-BuLi, THF, 78 C to rt, (2) 39.2, THF, 78 C to rt, (3) rt, 16 h; (b) UV irradiation (Hg mediumpressure lamp; I2, propylene oxide), toluene, rt, 3 h; (c) (1) excess neat BBr3, 4 days, 200 C, (2) MesMgBr, toluene/THF, 0 C, rt, 16 h.
a
Scheme 40. Synthesis of a P-Fused Double Helicenea
Reagents and conditions: (a)199 (1) 1-(2-methylnaphthyl) magnesium bromide, THF, 0 C, (2) rt, 1 h, (3) 80 C, 14 h, (40 I2, 0 C, (5) rt, 30 min;
(b) (1) n-BuLi, THF, Ar atm, 78 C, 1 h, (2) 0 C, 1 h, (3) bis(diethylamino)chlorophosphine, 78 C, (4) rt, 1 h, (5) S8, chlorobenzene, rt, 8 h,
(6) AlCl3, o-dichlorobenzene, 0 C, (7) rt, 8 h, (8) DABCO, 150 C, 12 h; (c) (1) m-chloroperoxybenzoic acid, DCM, 0 C, (2) rt, 14 h, (3) mchloroperoxybenzoic acid, DCM, 0 C, (4) rt, 10 h; (d) Et3P, o-dichlorobenzene, N2 atm, 60 C, 12 h.
for a range of substituted derivatives 38.8.195 Only two

regioisomers, 38.9 and 38.10, were observed among the
reaction products, and 38.9 was formed exclusively for electronwithdrawing R groups, such as CN or COMe.
The conversion of bisxanthylenes into helixanthenes is
associated with a signicant conformational change of the
nonplanar aromatic core. Bisxanthylenes typically exhibit a
thermally controlled equilibrium between an anti-folded and a
twisted conformer, which gives rise to thermochromism. In
contrast, helixanthenes are characterized by helicene-type
geometry. The structural change caused by the coupling was
employed in the design of a photoactive amphiphile 38.6,
reported in 2011 by Feringa et al.196 The latter species selfassembles into bilayers, with interdigitating hydrophobic chains
of the opposing amphiphiles. In the presence of phospholipids,
the bilayer forms vesicle-capped nanotubes. Upon irradiation
with ultraviolet light, which induces the photoconversion 38.6
into 38.7, these nanotubes are disassembled at a rate that is
dependent on the irradiation wavelength and light intensity. A
substituted helixanthene derivative, 38.11, synthesized in 2014
by Franceschin, Altieri, et al., revealed its potential for
stabilizing telomeric G-quadruplex DNA.197 The improved
selectivity of 38.11 was demonstrated using ESIMS data, in
vitro cancer screening, and specic immunouorescence assays.
A peripherally bis-B-doped bisanthene 39.5 was prepared in
2015 by Wagner and co-workers (Scheme 39).198 This species,
containing the 3,10-diboraperylene substructure, can alternatively be described as a doubly boron-bridged dibenzo[g,p]-
chrysene. 39.5 was prepared in a modular synthesis sequence

based on a Peterson olenation, followed by a stilbene-type
photocyclization, and a SiB exchange reaction. Unlike the
parent bisanthene, which is a NIR chromophore with the
absorption onset above 700 nm, 39.5 is an ecient blue
luminophore (em = 449, 475 nm, F = 0.78). Additionally, the
system was found to undergo reversible redox transitions both
in the cathodic and in the anodic regimes. The silyl derivative
39.1 used in the synthesis of 39.5 is a versatile starting material,
and was further employed for the preparation of smaller boroncontaining PAHs, 39.67.198
A doubly P-fused double helicene 40.3, structurally related to
the monophospha species 29.13 (vide supra), was obtained in
2014 by Nakamura, Hatakeyama, et al. (Scheme 40).199 The
key precursor, 2,3,5,6-tetraaryl-1,4-diiodobenzene 40.2, obtained by sequential arylationiodination of hexabromobenzene, was transformed into a bisphosphine, sulfurized, and
subjected to a tandem phospha-FriedelCrafts reaction,
providing 40.3 in a 10% overall yield. This compound easily
underwent desulfurization or oxidation, leading to compounds
40.5 and 40.4, respectively. 40.3 was characterized in the solid
state, showing a syn arrangement of the PS bonds and a
highly distorted inner benzene ring (bending angle of 23).
Despite this distortion, which leads to an apparent reduction of
aromaticity, the double helicene showed good thermal and
chemical stability.
3.1.3. Tetraheteraperylenes. The synthesis of a 1,2,7,8tetraazaperylene derivative 41.4a was reported in 1932 by
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Scholl et al.200 The diaroyl precursor 41.2a was synthesized by

reacting the bis(acyl chloride) 41.1 with m-xylene under
FriedelCrafts conditions. The reaction was however not
general, because of the competing formation of the dilactone
41.5a, which was typically the dominant product for other
arene reactants. 41.4a was then obtained from 41.2a by
reaction with hydrazine hydrate. An even larger product, 41.5,
was reported by the same group in subsequent work,201 while a
diaza system, 33.15 (Scheme 33), was similarly synthesized in
1980 by Gomes and Cabares.202 Pummerer and co-workers
reported the formation of 41.6, a -expanded 2,3,10,11tetraazaperylenoid, in a reaction of the corresponding
hexaketone with hydrazine hydrate.203
In 2014, this synthetic strategy was rediscovered by Zhang,
Feng, et al., who developed a more general and ecient route
to the diaroyl precursors, for example, 41.2bc (Scheme
41).204 It was found that the introduction of heteroatoms
Scheme 42. 7,8,15,16-Tetraazaterrylenea
Reagents and conditions: (a)205 lauric aldehyde, neat, 180 C, 1 h;

(b) TFA, reux, overnight; (c) hydrazine, HCl (cat.), BuOH, reux, 3
days.
a
donor/acceptor interface by Barnes et al.208 In that application,

they revealed high variability of emission properties, which was
proven to result from packing defects. TAT crystals exceeding
ca. 200 nm in width were observed to act as photoluminescence
waveguides and optical microcavity resonators.
Several tetraheteraperylene systems have been obtained by
various dimerization reactions of diheteraacene precursors.
Unexpected formation of pyridazino[4,3,2-kl:5,6,1-kl]diphenothiazine 43.2 was observed by Muller and co-workers
in an attempted BuchwaldHartwig arylation of phenothiazine
(Scheme 43).209 A Ni0-mediated coupling of the substituted
phenothiazine 43.1b was used by Yamamoto and Higashibayashi in the synthesis of the cyclodimer product 43.3b.210 The
dimer was nonplanar, forming a congested, slit-like cavity, and
could be oxidized to produce the buttery shaped dimer 43.4b
containing an inner NN bond. An analogous reaction
sequence was performed on the substituted acridone 43.1c,
yielding the diazaperylene product 43.4c. In 2015, Sakamaki,
Seki, et al. reported the synthesis of N-heterohelicenes
43.7ac, each containing a tetraheteraperylene core.211 These
systems were obtained from -expanded phenazine and
phenoxazine derivatives 43.5ac, which were initially oxidized
to cruciform dimers 43.6ac, which were then cyclized to
43.7ac using a stronger oxidant system. The double helicenes
showed highly nonplanar structures in the solid state, and were
found to be very stable toward racemization.
The 1,6,7,12-tetraazaperylenoid eilatin (44.5), a bright
yellow alkaloid rst described by Kashman et al. in 1988, is a
remarkable example of a natural product containing an
extended benzenoid fusion pattern.212,213 The compound was
isolated in minute amounts (up to 0.001% of dry weight) from
the Red Sea tunicate Eudistoma sp. Eilatin, and its analogues or
complexes have been intensely studied for their potent growth
regulatory properties and ability to aect cell shape and
adhesion,214 their anti-HIV activity and RNA binding,215,216 as
well as antimalarial and antitrypanosomal potential.217,218 The
rst total synthesis of eilatin was published in 1993 by Kubo
and co-workers,219 who compared two synthetic pathways, each
starting from a 4-phenylquinoline-5,8-dione derivative bearing,
respectively, a nitro or triuoroacetylamino substituent (44.1 or
44.6, Scheme 44). Compound 44.1 was converted regioselectively into 6-(2-acetylanilino)-4-(2-nitrophenyl)quinoline5,8-dione (44.2). In the next two steps, tetracyclic (44.3)
and pentacyclic (44.4) intermediates were obtained. In the last
step, catalytic hydrogenation of the NO2 group followed by
cyclization aorded eilatin. The second pathway started with
Scheme 41. 1,2,7,8-Tetraazaperylenes and Related Systemsa
a
Reagents and conditions: (a)200 m-xylene, FeCl3, reux; (b)204 CrO3,
AcOH/water, 75 C, 1.5 h; (c)200 hydrazine hydrate, toluene, reux;
(d)204 hydrazine hydrate, EtOH, 78 C, 2 days.
results in a pronounced blue shift of the electronic spectra of

the alkyl substituted tetraazaperylenes (such as 41.4b) in
comparison with perylene, but this eect could be oset by
means of aryl substitution (e.g., in 41.4c), to produce an overall
red shift. All tetraazaperylene derivatives showed very weak
uorescence, typical of N-doped acenes, in contrast to the
undoped perylene.
7,8,15,16-Tetraazaterrylene (TAT, 42.3, Scheme 42) was
synthesized in 2012 by Wudl et al.205 Their three-step synthesis
began with a thermally induced condensation of phenalene-1,3dione with lauric aldehyde. The resulting product, 42.1, was
subjected to an acid-catalyzed dehydrative cyclization, to yield
the xanthenedione system 42.2. The latter intermediate was
condensed with excess hydrazine, undergoing an extrusion of
the internal methylene bridge. In subsequent work, the
electronic structure of TAT derivatives was investigated
theoretically by Wang et al.206 The aggregation behavior of
42.3 was explored in solution and in the solid state by Spano et
al.,207 showing a unique HJ-aggregate behavior. TAT single
crystals coated with pentacene were used as a photovoltaic
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showed that eilatin forms octahedral complexes with osmium,

capable of dimerization via stacking, and that the
nonequivalence of binding sites allows the selective synthesis
of both mono- and binuclear complexes.224,225 Investigations of
mononuclear complexes of isoeilatin226228 and dibenzoeilatin229,230 also revealed the formation of discrete dimers in
solution and in the solid state, which were stabilized by weak
stacking interactions between ligands.
In 2002, Tor and Glazer showed that ruthenium complexes
of 1,6,7,12-tetraazaperylene and its two benzologues, including
eilatin (44.1944.21), could be prepared using the dehydrogenative approach described above for 32.4 (Scheme 32).138
The free 1,6,7,12-tetraazaperylene 44.18 was synthesized by
Holdt et al. in 2012 by anionic radical coupling of 1,1-bis-2,7naphthyridine (44.17).231 Mono- and binuclear complexes of
44.18 with ruthenium(II) were then obtained under mild
reaction conditions.
The syntheses of 44.1844.21 represent two oxidative
approaches available for the construction of heteraperylene
cores, that is, anionic radical coupling and catalytic dehydrogenation, both of which involve intramolecular ring closures. A rare
example of an intermolecular oxidative coupling was provided
in 2007 by Cushman et al.,232 who showed that aerial oxidation
of 2,7-naphthyridine-1,3,6,8-tetraol 44.22, available from a
simple one-step synthesis,233 leads to the formation of the
highly oxygenated 2,5,8,11-tetraazaperylenoid 44.23. The latter
species was found to be a competitive inhibitor of lumazine
synthase, signicantly more potent than the monomeric 44.22.
Recent research on BN-doped graphenoids provided two
examples of tetraheteraperylenoid structures (for related
pyrenoid systems, see Scheme 95, section 4.2). 5b,7b-Diaza3b,9b-diborabenzo[ghi]perylenes 45.4bc with a doubly
buttressed B2N2C2 core were obtained in 2010 by Piers and
co-workers (Scheme 45).234 The assembly of the perylenoid
core was accomplished by condensing a chelating Lewis acid,
2,2-diborabiphenyl 45.2, with 2,6-bisalkynyl-substituted pyridazines 45.1ac. This step, which led to the simultaneous
formation of two BN bonds and one CC bond, yielding
45.3ac, was followed by a Pt-catalyzed CC bond closure,
which however was only eective in the presence of terminal
alkyne substitution. As part of their eort to make a borazineembedded HBC analogue (cf., Scheme 17, section 2.3),
Bettinger and co-workers reported in 2014 the photochemical
cyclization of 1,2:3,4:5,6-tris(o,o-biphenylylene)borazine 45.5,
which yielded the singly coupled product 45.6.235 45.6
underwent solvolysis with methanol, producing the B2N2
product 45.7, which was shown to have an essentially planar
structure in an X-ray crystallographic analysis.
Scheme 43. Tetraheteraperylenoids via Dimerization of

Diheteraacenesa
Reagents and conditions: (a)209 2-bromomesitylene, Pd2(dba)3dba,

P(t-Bu)3HBF4, t-BuOK, THF, MW, 150 C, 15 min; (b)210 Ni(cod)2,
bpy, cod, THF, 5080 C; (c)210 (1) DDQ, (2) hydrazine; (d)210 tBuOK, rt, 4 h; (e)211 DDQ, DCM; (f)211 DDQ, Sc(OTf)3, DCM, 19%
for all derivatives; (g)211 (1) DDQ, DCM, (2) DDQ, Sc(OTf)3, DCM,
14% for 43.7a, 10% for 43.7c.
a
the synthesis of pyridoacridinone 44.7, which was cyclized to

44.8, and subsequently converted to eilatin by a one-pot
annulation of ring G. Kashman et al. proposed a synthesis of
eilatin using a biomimetic two-step procedure.220 Starting from
catechol and protected kynuramine under oxidative conditions,
1,2-acridinedione derivative 44.9 was obtained in the rst step.
Next, upon treatment with boron triuoride diethyl etherate,
44.9 was converted into 44.10. Eilatin was prepared from 44.10
or directly from 44.9 using basic conditions.
In 2015, Plodek and Bracher proposed a synthesis of eilatin
starting from the readily available 9-methyl-3,4-dihydroacridin1(2H)-one 44.11.221 This compound was converted into
pyridoacrid-4-one (44.13), the key intermediate, which
represents the common substructure of many pyridoacridine
alkaloids. Starting from 44.11, it was also possible to prepare
pyridoacrid-6-one isomeric to 44.13, which was used as a
precursor of isoeilatin 44.14. Earlier, Kashman et al. proposed a
synthesis of isoeilatin starting from an 1,4-acridinedione
isomeric with the 1,2-dione 44.9.222 In the same work,
dibenzoeilatin 44.16 was obtained by acidic treatment of
compound 44.15.
Eilatin and its analogues containing the 1,6,7,12-tetraazaperylene core can be viewed as potential bifacial ligands. In 1997,
Kashman, Kol, et al. showed that 44.5 prefers to bind metals to
its less hindered face, by preparing two ruthenium complexes.223 Further research carried out by Kol and co-workers
Heteroannulation of one or two bay regions of the perylene

core has been highly investigated, with synthetic eorts
focusing mostly on perylene itself and on its mono- and
diimides. These investigations are rationalized by the eect of
such annulation on the photophysical properties of these
materials (for a theoretical analysis, see a 2008 paper by Zhao
and Han236). A practical strategy for the preparation of
[ghi]annulated perylenes 46.24 in good yields was described
by Wang et al. in 2008 (Scheme 46).237 The strategy was based
on earlier work by Langhals and co-workers, who synthesized a
range of variously substituted pyrrolo- and thieno-annulated
PMI and PDI derivatives 46.710.238,239 The crucial step of
Wangs synthetic pathway was the ecient preparation of 1AJ
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Scheme 44. Synthesis of Eilatin and Related Systemsa
Reagents and conditions: (a)219,221 CeCl37H2O, 2-aminoacetophenone, EtOH, 3 h, rt; (b)220 10% H2SO4 in AcOH, 15 min, 60 C; (c) (1) DMF
diethyl acetal, DMF, 30 min, 120 C, (2) NH4Cl, AcOH, 30 min, 115 C; (d) H2 (1 atm), 10% Pd/C, 1.5 h; (e)220 BF3Et2O, DCM, 24 h, rt; (f)
NH3, MeOH; (g) NH3, MeOH, 4-dimethylaminopyridine (cat.); (h)221 (1) DMF diethyl acetal, DMF, 30 min, 55 C, (2) NH2OHHCl, AcOH, 1
h, 100 C; (i) (1) acetic anhydride, 2 h, 50 C, (2) 10% NaOH in H2O/MeOH, 2 h, 80 C, (3) MnO2, toluene, reux; (j) 10% H2SO4 in AcOH, 20
min, 90 C; (k) (1) DMF diethyl acetal, DMF, 30 min, 120 C, (2) NH4Cl, AcOH, 1 h, 120 C; (l)222 AcOH:H2SO4:triuoroacetic acid (45:10:45),
40 min, 60 C; (m)231 (1) potassium, dimethoxyethane, N2 atm, 12 h, reux, (2) air, THF, 6 h; (n)232 (1) EtOH, diethylamine, rt, 48 h, (2) H2SO4
(70%), 100 C, 10 min; (o) DMSO, air, rt, 1 month.
a
Zhu and co-workers studied semiconducting properties of

the S-annulated perylene 46.2 (Scheme 46) as a potential
organic eld-eect transistor (OFET).243,244 The X-ray analysis
of a 46.2 single crystal revealed stacking along the b axis with
intermolecular distances of 3.47 , with short distances (3.51
) between sulfur atoms of neighboring columns related by an
inversion center. This material exhibited a high mobility of up
to 0.8 cm2 V1 s1 measured for transistors based on an
individual single-crystal wire and 0.05 cm2 V1 s1 for spincoated thin lms.243 On highly oriented polyethylene thin lms,
the S-annulated perylene 46.2 was processed into lathlike
crystals using vapor phase epitaxy.244 Wang, Hu, and coworkers described single-crystalline microribbons of the Seannulated perylene 46.3, which were prepared by drop casting
and physical vapor transport techniques.245 Single-crystal
transistors, fabricated by the gold layer glue technique,
showed mobilities approaching 2.66 cm2 V1 s1. Crystals of
nitroperylene 46.1, which formed alongside the 3-nitro isomer.

Chalcogen-annulated perylenes 46.2 and 46.3 were then
obtained by heating 46.1 with elemental sulfur and selenium,
respectively. Perylenothiophene 46.2 had been prepared earlier
by several groups, using harsh reaction conditions.240242 An
extension of the above synthesis, which included the
benzannulation of the other bay region in 46.1, was used to
produce the benzo derivative 46.6. Phenanthro[1,10,9,8cdefg]carbazole 46.4 was synthesized by Wang et al. using the
Cadogan reaction with triethyl phosphite.237 When performed
in the perylene bay region, the Cadogan reaction is likely
associated with an increase in internal strain. Consequently, an
attempted bis-annulation of the dinitro derivative 46.11
produced only the singly annulated product 46.12.238 In the
solid state, perylenes 46.24 adopt planar conformations, but
their crystal packing shows marked dependence on the identity
of the annulated heteroatom.
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Scheme 46. Synthesis of [ghi]Heteroannulated Perylenoidsa
Scheme 45. Synthesis of BN-Containing

Tetraheteraperylenesa
a
Reagents and conditions: (a)234 toluene, 25 C, 48 h; (b)234 PtCl2,
100 C, 24 h; (c)235 I2, h, THF, dry toluene, 16 h; (d)235 DCM,
MeOH, 70 h.
46.3 revealed a near planar conformation with regular

stacking. The observed SeSe contacts of 3.49 were
considered responsible for the observed ecient carrier
transport.
A dierent route to the benzo[6,7]peryleno[1,12-bcd]thiophene ring system 47.3 was developed in 1975 by Wynberg
et al. in the course of their work on dehydrohelicenes (Scheme
47, for related circulene derivatives, see Scheme 157).246,247
The helicene 47.1 underwent a ring closure to yield 47.2, when
heated at 140 C in the NaClAlCl3 melt. Compound 47.2 was
then converted into 47.3 via the DielsAlder addition of maleic
anhydride followed by anhydride cleavage. 47.3 was oxidized to
sulfone 47.4 with m-chloroperoxybenzoic acid in methylene
chloride.
Phenanthrocarbazole 46.4, typically called N-annulated
perylene (NAP), is a valuable heteroaromatic building block
for materials chemistry applications because of its favorable
electron-donating properties and the availability of a
functionalizable nitrogen. The latter site is typically alkylated
in the presence of a base, although a Ru-catalyzed dehydrogenative N-arylation was recently reported (Scheme 48).248 46.4 is
readily brominated at positions 3 and 10, opening a convenient
path for further functionalization.
Wu et al. synthesized several N-annulated derivatives 49.1a
d (Scheme 49) possessing variable electron-decient subunits,
for use as acceptordonoracceptor dyes.249 These systems
showed tunable absorptions in the visible range and ecient
emission that extended into the NIR region. Wang and coworkers reported a series of diarylamino-functionalized Nannulated perylenes containing dierent electron-acceptor
segments: cyanoacrylic acid (49.2a), benzothiadiazolebenzoic
acid (49.2b), and pyridothiadiazolebenzoic acid
(49.2c).250,251 Dye-sensitized solar cells employing 49.2ac
showed power conversion eciencies (PCEs) of 5.08.8% at
air mass 1.5 global (AM1.5G) conditions. Further increase in
PCE values was achieved by introducing an alkoxyphenyl group
in the donor part of the dye. In particular, the ethynylbenzothiadiazole-benzoic acid derivative 49.3b yielded a PCE of
Reagents and conditions: (a)237 fuming HNO3/H2SO4, 1,4-dioxane,

60 C, 2530 min; (b) sulfur powder, NMP, 180 C, 5 h; (c) Se
powder, NMP, 180 C, 5 h; (d) triethyl phosphite, reux, 2 h; (e) (1)
diethyl maleate, 180 C, 5 h, (2) chloranil, 180 C, 24 h; (f) sulfur
powder, NMP, 180 C, 5 h; (g)238 triethyl phosphite, reux, 1 h 40
min.
Scheme 47. Benzo[6,7]peryleno[1,12-bcd]thiophenea
Reagents and conditions: (a)246 NaCl, AlCl3, 15 min, 140 C; (b)247

(1) maleic anhydride, chloranil, 2 h, reux, (2) soda lime, N2 atm, 1 h,
370 C; (c) m-chloroperoxybenzoic acid, DCM, 5 h.
a
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tion, and enabled the successful preparation of the diimide

derivative 50.7.255 A range of bis-N-annulated quaterrylenes
were subsequently prepared using the above protocol,256258
some of them showing self-assembly behavior as supramolecular nanotapes257 and columnar liquid crystals.256 BisN-annulated quaterrylenes are strongly absorbing, uorescent
dyes, with emission maxima in the 700800 nm range.
In 2014, Wu et al. reported the synthesis of an s-indacenebridged quinoidal perylene dimer 50.6 (Scheme 50).258
Compound 50.6 was obtained form diol 50.4, which was
cyclized to the 50.5 intermediate in the presence of boron
triuoride and subsequently dehydrogenated with DDQ.
Compound 50.6 exists as a closed-shell quinoid with an
intramolecular charge-transfer character. It showed shorter
singlet excited-state lifetimes, stronger two-photon-absorption,
and a smaller energy gap than a corresponding bis-N-annulated
quaterrylene derivative.
The synthetic paradigm used to assemble quaterrylene 50.3
was rened in 2010 by Wang et al., to enable the synthesis of
tri-N-annulated hexarylenes 50.8ac.259 The terperylene
precursors were assembled using Suzuki cross-coupling and
subsequently cyclodehydrogenated using Sc(OTf)3/DDQ to
yield 50.8ac. Electronic absorptions of 50.8ac are very
intense and bathochromically shifted with respect to lower
rylene homologues (to ca. 846 nm). Compounds 50.8ac
exhibit remarkably large dipole moments, which are likely
responsible for stabilization of -stacked H-aggregates. The
aggregation of 50.8ac was inferred from the concentration
and substitution dependence of their electronic spectra, which
could be rationalized using vibronically resolved TD-DFT
calculations.
In 2013, an iterative synthetic scheme based on Suzuki
Miyaura cross-coupling was employed by Wu and co-workers
to assemble NAP oligomers 51.1bf in a length-selective
Scheme 48. Ru-Catalyzed N-Arylation of

Phenanthro[1,10,9,8-cdefg]carbazolea
Reagents and conditions: (a)248 4-methyl-N-phenylaniline, [{(pcymene)RuCl2}2], Cu(OAc)2, cumene/tetrachloroethylene/AcOH,

O2, 150 C, 24 h.
10.4%.252 An even higher value (12.5%) was reported for the

N-annulated indenoperylene derivative 49.6.253 The latter
compound was obtained in ve steps from ester 49.4. The
indene unit, installed to enforce coplanarity in the donor
segment, was constructed by a double Grignard addition
reaction with (4-hexylphenyl)magnesium bromide, followed by
the acid-catalyzed cyclization of the resulting tertiary alcohol.
In 2009, Li and Wang proposed an ecient synthetic method
toward a processable bis-N-annulated quaterrylene 50.3
(Scheme 50).254 50.3 was obtained in one step by reacting
compound 50.1 with 5 equiv of DDQ and scandium
trifuoromethanesulfonate in 23% yield. Interestingly, a
signicantly higher yield was achieved in a two-step variant of
this synthesis, involving sequential oxidation with 1 and then 5
equiv of the DDQ/Sc(OTf)3 reagent. Under these conditions,
the terminal naphthyl substituents would not undergo oxidative
dehydrogenation in either 50.3 or its monoperylene analogue.254 An alternative approach, developed almost concurrently by Wu and co-workers, combined Yamamoto
homocoupling with a K2CO3/ethanolamine oxidative annulaScheme 49. N-Annulated Perylene Dyesa
Reagents and conditions: (a)253 (1) (4-hexylphenyl)magnesium bromide, THF, reux, overnight, (2) Amberlyst 15, toluene, reux, overnight.
AM
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Scheme 50. N-Annulated Bis-perylene Dyesa
Reagents and conditions: (a)254 (1 equiv) DDQ, Sc(OTf)3, toluene, 25 C, 10 min; (b) (5 equiv) DDQ, Sc(OTf)3, toluene, 50 C, 24 h; (c)258
BF3Et2O, dry DCM, rt, 10 min; (d) (2 equiv) DDQ, dry toluene, 85 C, overnight.
a
manner (Scheme 51).260,261 51.1bf and their parent

monomer 51.1a were then converted into the extended
tetracyanoquinodimethanes 51.2af by the application of the
Takahashi coupling reaction with malononitrile, followed by
either aerial or chloranil-mediated oxidation.260 In subsequent
work, this transformation was applied to the fully condensed
rylenes 51.3ab, to yield the corresponding quinodimethanes
51.4ab.261 Both classes of quinone oligomers showed a clear
chain-length dependence of their photophysical and electrochemical properties. The nonfused series exhibited tunable
ground-state structures: a closed-shell singlet for 51.2a, openshell singlet for 51.2bd, and triplet biradical for 51.2ef.260
Analogously, the ground-state electronic structures in the fully
fused series changed from a closed-shell singlet for 51.4a to an
open-shell singlet biradical for 51.4b. Both of the latter
compounds revealed a very strong one-photon (OPA) and twophoton (TPA) absorption response in the NIR range, due to
the extended -conjugation, as well as a singlet biradical
character.261 Thiophene-extended analogues 51.5ab were
shown to possess singlet biradical ground states with small
singlettriplet energy gaps.262 Similar reaction sequences were
used in 2015 by Wu et al. to prepare another series of push
pull type quinoidal perylene oligomers, 51.8ad.263 These
compounds possessed a ground-state electronic structure with a
balanced contribution from closed-shell quinoidal, open-shell
diradical, and closed-shell zwitterionic resonance forms. As a
result, their ground states and physical properties showed a
clear chain length and solvent polarity dependence. For
example, it was found that with the extension of the chain
length, the diradical character greatly increased, while the

contribution of the zwitterionic form diminished. Solvent
polarity played a major role in controlling the ground state and
physical properties of the monomer, with a smaller eect on the
dimer and trimer.
In 2010, Wu and co-workers reported the synthesis of two Nannulated perylene systems containing one (52.1) or two
(52.2) fused porphyrin units (Scheme 52). 264 These
compounds were synthesized by means of Sc(OTf)3/DDQmediated oxidative cyclizations of appropriate meso-linked
porphyrin precursors. These hybrid molecules are highly
soluble in common organic solvents and exhibit intense NIR
absorption, showing principal Q bands at 775 and 952 nm,
respectively. Importantly, both compounds revealed detectable
photoluminescence, with quantum yields of 5.6% and 0.8% for
52.1 and 52.2, respectively. Subsequent work on NAP
porphyrin hybrids as materials for dye-sensitized solar cells was
reported by the groups of Wang and Wu.265 Compounds 52.5a
and 52.5b exhibited power conversion eciencies of 10.3% and
10.5%, respectively, comparing favorably with the eciency of
the YD2-o-C8 porphyrin benchmark (12.3%).266 Because of
inecient -conjugation between the segments in compound
52.3 and the low-lying LUMO energy level and nondisjointed
HOMO/LUMO proles in 52.4, these compounds exhibited
signicantly lower power conversion eciencies of 5.6% and
0.3%, respectively. Using an analogous oxidative coupling
strategy, the Wu group synthesized peri-fused hybrids 52.7ab
consisting of NAP and boron dipyrromethene (BODIPY)
subunits.267 52.7b has its principal absorption band at 670 nm
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Scheme 51. Synthesis of Tetracyano Derivatives of N-Annulated Rylenesa
Reagents and conditions: (a)260 (1) malononitrile, NaH, Pd(PPh3)2Cl2, reux, 48 h, (2) 2 M HCl, (3) p-chloranil, CHCl3, rt; (b) (1) malononitrile,
NaH, Pd(PPh3)2Cl2, reux, 48 h, (2) 2 M HCl, air; (c)261 (1) malononitrile, NaH, Pd(PPh3)2Cl2, reux, (2) 2 M HCl, 05 C, air.
and shows relatively weak, solvent-dependent photoluminescence in the 700860 nm range. Related work on N-annulated
peryleneporphyrin tape hybrids is discussed in section 7.3.
Yu et al. synthesized a donoracceptor copolymer C9.1,
containing N-annulated perylene blocks, with the aim of
extending the -conjugation across the polymer main chain
(Chart 9).268 Solution-processed eld-eect transistors based
on C9.1 exhibited a high hole mobility value of up to 0.30 cm2/
(V s) and a current on/o ratio above 105. Kim and co-workers
prepared NAP copolymers C9.2 and C9.3 containing dierently substituted dithienylquinoxaline subunits.269 Both polymers showed similar physical properties: broad absorption in
the 400700 nm range, optical bandgaps of 1.8 eV, and the
appropriate frontier orbital energy levels for ecient charge
transfer separation at polymer/PC71BM interfaces. When used
in sensitized solar cells, these materials showed PCE values of
up to 3.3%.
Donor-linked NAP derivatives C10.12 containing a
doubled polycyclic core were investigated by the groups of
Fu and Wang (Chart 10).270 In contrast to the NAP systems
described above, C10.12 were -extended in the bay
direction. In both molecules, the donor units (triphenylamine
or tetraphenylporphyrin) were installed by bay annulation of
the corresponding amines under Pd-catalyzed conditions.271,272
In these systems, uorescence quenching due to intramolecular
charge transfer was observed, with the rate of charge separation
reaching 1012 s1 in DCM. A PEGylated bis-NAP system C10.3
was used by Wang, Chen, et al. as a nonporphyrin PDT
photosensitizer, showing a high eciency of singlet oxygen
generation ( = 0.66).273
Chalcogen-annulated perylenes have been less studied than

their N-annulated counterparts. An early example of a sulfurcondensed perylenoid was provided by the synthesis of
dibenzo[5,6:7,8]pentapheno[13,14-bcd]thiophene 53.2
(Scheme 53), rst reported by Steinkopf in 1935.274 53.2,
named avophene after its orange-yellow color, was obtained
by cyclodehydrogenation of tetraphenylthiophene 53.1, a
procedure subsequently rened by Sasse and co-workers.275
Desulfurization of 53.2 with Raney nickel produced dibenzoperylene 53.3 in moderate yield.275 The mechanism of
potassium-induced desulfurization of 53.2 was investigated in
1999 by Rabinovitz et al.276 Zander and Franke reported an
alternative route to 53.2 involving sequential thermal
desulfurizationdehydrogenation of tetrabenzothianthrene
53.4.277 They additionally showed that the thiophene ring
could be reintroduced to 53.3 using direct reaction with
elemental sulfur. An analogous reaction, performed with Se
powder, yielded the Se-annulated 53.6.278 A low-yielding
synthesis of the furan analogue 53.8, reported by Zander,
employed heating the dione 53.7 with elemental Cu.279
Compound 53.9, a dienone derivative of 53.8, was proposed
by Clar as an oxidation product of 53.3,280 but its structure was
not supported by later work.281,282
Benzo[6,7]peryleno[1,12-bcd]thiophene 53.12 (thiacoronene) was synthesized during the 1970s by Boekelheide and
co-workers in the course of their work on bridged [18]annulenes.283,284 53.12 was obtained from cyclophane 53.11 by
UV irradiation in the presence of air. The reaction proceeded
through the cycloadduct 53.10, which could be observed using
NMR upon irradiation of a degassed solution of 53.11.
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Scheme 52. N-Annulated PeryleneOligopyrrole Hybridsa
Reagents and conditions: (a)265 FeBr3, DCE, 29%; (b)267 FeCl3, DCM, 23% for 52.7b.
Chart 9. Copolymers Containing N-Annulated Perylene Units268,269
In 2012, Reau et al. reported the synthesis of P-annulated

perylenes with tunable optical properties (Scheme 53).285
Compound 53.15b was obtained alongside the incompletely
fused 53.14b by using photochemically induced cyclodehydrogenation of the dibenzo[e,g]isophosphindole sulde derivative 53.13b. Both fused products were air-stable and soluble
in common organic solvents. 53.15b was transformed into the
air- and moisture-stable phospholium salt 53.16 by treatment
with methyl triate. Finally, a reaction with the nucleophilic
phosphane P(NMe2)3 converted 53.16 into 3,3-dibenzophosphapentaphene 53.17. Electronic absorptions of charged
derivatives of 53.17, such as 53.16, showed marked bathochromic shifts, which were accordingly reected in the
emission properties of these systems. In subsequent work,
Nyulaszi, Hissler, et al. described an analogous synthesis of the
corresponding P-oxides 53.14a and 53.15a, which however
formed less eciently. 286 The electronic structure of
heteroannulated perylenoids such as 53.6, 53.8, and 53.17
was investigated theoretically by Hissler, Nyulaszi, et al.287
A doubly S-annulated perylene diimide 54.2 was described in

2006 by Wang, Zhu, and co-workers.288 The two thiophene
rings in 54.2 were obtained in a Stille-type coupling reaction
between the tetrachloro PDI derivative 54.1 and bis(tributyltin)sulde (Scheme 54). In contrast to 54.1, in
which the PDI core is highly twisted because of steric
repulsions between adjacent Cl atoms, 54.2 shows a planar
conformation in the solid state. The reduction of strain may
therefore be a contributing driving force in the synthesis of 54.2
(for a related example, cf., Scheme 21, section 2.4). The above
bis-annulation was also applicable to bis-PDI system 54.3.289 In
addition to the doubly S-annulated system 54.4b, analogous to
54.2, the Wang group prepared the bis-N-annulated species
54.4a by means of the BuchwaldHartwig amination reaction.
Both compounds exhibit nonplanar conformations, each with
two bowl-shaped units of opposing curvatures, as shown by the
X-ray structural analyses. The highest local curvature,
corresponding to a POAV angle of 4.7, was found in 54.4a.
The absorption spectra revealed a marked red shift of the
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Chart 10. Bay-Expanded NAP Derivatives270,273
Double S-annulation of an otherwise unmodied perylene

was accomplished by Wang, Shuai, Pei, et al. in 2010.290
Peryleno[1,12-bcd:6,7-bcd]dithiophene 54.7 was obtained in
three steps with an 8% overall yield (Scheme 54). After the
initial mononitration of 46.2 with an excess of HNO3/H2O, the
resulting 54.5 was converted into the dithiine intermediate 54.6
in a reaction with sulfur powder. In the nal step, 54.6 was
subjected to copper-mediated partial dechalcogenation. 54.7 is
a solution-processable semiconductor, from which highperformance 1D single-crystalline nanoribbon transistors were
fabricated, with mobilities of up to 2.13 cm2 V1 s1 measured
for individual nanoribbons. The integration of two sulfur atoms
into the perylene skeleton induces a compressed, highly
ordered packing mode directed by SS interactions. In 2014,
Li, Mullen, and co-workers described a synthetic pathway to the
doubly S-annulated 3,4,9,10-tetrabromoperylene 54.11.291
Their reaction sequence involved the Stille S-coupling
annulation, followed by cyclization to the respective anhydride
54.10 and conversion of the latter compound into the
tetrabromo target 54.11 using the Hunsdiecker reaction.
Phenanthro[1,10,9,8-klmna]phenanthridine 55.3, a pyridofused perylene derivative, was reported in 1972 by Shine and
Ristagno.292 It was formed, in addition to 1-deuterioperylene
55.2, in a reaction of 1-cyanoperylene 55.1 with LiAlD4
second allowed electronic transition associated with the

presence of ve-membered rings in the fused system.
Scheme 53. Heteroannulated Perylenoidsa
Reagents and conditions: (a)275 AlCl3, NaCl, 130 C, dry air, 5 h; (b) Raney Ni, mesitylene, MeOH; (c)277 S powder, 320 C, 30 min, 17%; (d)
Cu, 430 C, 35%; (e) Cu, 500 C; (f)278 Se powder, 380 C, 14 h; (g)279 Cu powder, heating; (h)284 degassed THF-d8, 80 C, 253.7 nm; (i) THFd8, air, rt, 253.7 nm, 100%; (j)285 I2, h, toluene, 20 h; (k) MeOTf, DCM; (l) P(NMe2)3, DCM.
a
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Scheme 54. Doubly Bay-Annulated Perylenesa
Reagents and conditions: (a)288 Bu3SnSSnBu3, Pd(PPh3)4, toluene, reux, 10 h, 72%; (b)289 Pd(OAc)2, PCy3, PhNH2, KOtBu, toluene, reux, 5 h,
51%; (c)289 Bu3SnSSnBu3, Pd(PPh3)4, toluene, reux, 12 h, 68%; (d)290 HNO3/H2O, 1,4-dioxane, 60 C, 510 min, 15%; (e)290 sulfur powder, Nmethyl-2-pyrrolidone, 180 C, 5 h, 61%; (f)290 copper nanopowder, 250280 C, 1 h, under argon, 88%; (g)291 Bu3SnSSnBu3, Pd(PPh3)4, toluene,
under Ar, reux, 24 h, 66%; (h)291 KOH, 2-propanol, water, reux, overnight, 98%; (i)291 bromine, 1 M NaOH, water, 10 min, 30 C, 89%.
56). The N-doped species 56.7a was obtained in 2006 by

Benniston and Rewinska294 in a multistep synthesis, with an
overall yield below 5%. Their work was based on a much earlier
extensive report by Dilthey et al., published in 1939, which
described the synthesis of ortho-fused precursors 56.6, 56.8,
and 56.10, and their presumed conversion into singly coupled
perylenoid products.297 In the rst step, the three-component
condensation of N-phenyl-2-naphthylamine, benzaldehyde, and
2-naphthol in glacial acetic acid produced 56.4.294 Oxidation of
this intermediate with MnO2 yielded the light-sensitive carbinol
56.5, which was converted into the fully aromatized
hexauorophosphate salt 56.6a. In the presence of ambient
light, 56.6a was found to convert to the doubly fused species
56.7a, rather than to the singly fused product proposed by
Dilthey et al.297 In a modied synthetic route, described in
2008 by Mullen and co-workers, acridinium intermediates 56.6
were obtained by reuxing 56.8a or 56.8b with appropriate
amines, and subsequently photocyclized to 56.7be.295
Derivatives 56.7b and 56.7e were found to self-assemble into
nanoscale wire-like bers and helical aggregates, respectively.
Oxygen- and sulfur-containing cations, 56.9be and 56.11,
were described in 2009 by Mullen and co-workers.296 The
photocyclization of 56.8be under 300 nm UV light led to the
fused xanthenium salts 56.9be, and a sulfur analogue, 56.10,
was prepared in a similar fashion (Scheme 56). The work
revealed that optoelectronic properties of these xanthylium and
thioxanthylium salts are strongly dependent on the heteroatom
incorporated into the core. Ordered columnar liquid crystalline
phases were observed for di- and tridodecyl-substituted salts
56.9ce. X-ray scattering data and molecular modeling
indicated that in each mesophase, three molecules selfassembled into a disclike structure, and the resulting discs
were further stacked into columns to ultimately yield hexagonal
columnar phases.
(Scheme 55). A related structure, 55.4, was proposed in 1970

by Zander and Franke as a possible pyrolysis product of Scheme 55. Perylenes with Bay-Fused 6-Membered Hetero
Ringsa
Reagents and conditions: (a)292 LiAlD4, THF, 4 h, 54%.
anthramine hydrochloride.293 A tetraester derivative 55.5 was

synthesized in 2012 by Cheng, Xiao, and co-workers in the
course of their work on Schi-base diazacoronenes (Scheme 3,
section 2.1).63 Similarly, the work of Wang et al., targeting bisimidazolo-fused coronenes, led to the synthesis of the singly
fused perylenoid 55.6.64
A range of cationic 14-heteraphenanthro[2,3,4,5-pqrab]perylenes have been reported, containing nitrogen
(56.7),294,295 oxygen (56.9),296 or sulfur296 (56.11, Scheme
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Scheme 56. Synthesis of 14-Heteraphenanthro[2,3,4,5-pqrab]perylenesa
Reagents and conditions: (a)294 glacial AcOH, reux, overnight; (b) MnO2, glacial acetic anhydride, bubbled with HCl, protected from light, reux,
1 h; (c) (1) conc. HCl, glacial AcOH, 5 min, (2) Et2O, (3) KPF6 (aq); (d) MeCN, air, h, several hours; (e)295 aniline/amine, THF, argon atm,
reux, 6 h; (f) EtOH, h, rt, 24 h; (g)296 AcOH, 300 nm, rt, 24 h; (h) DCM, UV irradiation (300 nm), rt, 24 h.
core, and prepared two types of nitrogen-doped derivatives,

58.2 and 58.3 (Scheme 58).305 The 58.2 polymer was
synthesized by the Suzuki coupling reaction between a pyrazine
linker and a 2,6-disubstituted naphthalene followed by
cyclodehydrogenation. By using equimolar amounts of pyrazine
and benzene linkers for polymerization, a nonregioregular
polymer 58.3 with 50% N-doping was obtained. The electron
mobility of the graphene nanoribbons increased while the hole
mobility decreased, with the increasing amount of nitrogen
doping. This relationship indicated that N-doping changed the
charge-transport behavior of these graphene nanoribbons from
ambipolar to an n-type semiconductor. The threshold voltage
of the graphene nanoribbons shifted from 20 to 6 V upon
increasing the amount of nitrogen doping.
A range of systems containing a hetero ring fused to the 1,2
edge of benzo[ghi]perylene have been synthesized, typically by
fusion of a heterocyclic substituent to the bay region of a PDI
or a perylene tetraester (for a relevant phthalocyanine
derivative, see Scheme 193, section 7.1). Pyridine-fused
benzoperylenes C11.12 (Chart 11) were obtained by Wang
and co-workers in a manner analogous to that of the
corresponding bispyrido-fused coronenes (see Scheme 23,
section 2.5).106 Triazole-fused benzoperylenes C11.3a4a,
bearing dierent generations of Newkome dendrimers, were
assembled with the aid of the Huisgen reaction by Hirsch et
al.107 In comparison with the bis-fused coronene analogues
(section 2.5), the photochemical electrocyclization reaction
leading to benzoperylene C11.3a occurred faster (3090 min),
apparently for steric reasons. The terminal t-butyl groups of the
dendron appendages in C11.3a4a were cleaved with TFA in
nearly quantitative yields to produce water-soluble derivatives
C11.3b4b.
The above strategy could be extended to larger fused
heterocycles and to the formation of heterocycle-bridged bisperylene molecules. In 2010, Yuan, Xiao, and Qian reported a
photochemical synthesis of octaester C11.5, with a thieno[3,2b]thiophene linker embedded between the two perylene
The fusion of a pyrazine ring in the bay region of perylene

was rst achieved in 1949 by Zinke, who obtained the
dibenzoperylene derivative 57.2 by condensing the 57.1 dione
with hydrazine (Scheme 57).298 57.2 was also prepared by
photochemical cyclodehydrogenation from 3,4,5,6-tetraphenylpyridazine 57.3299 and by reaction of 53.3 with diazenedicarboxylates73 or with cyclic hydrazides.300 The oxidative
cycloaddition approach was eective in preparing derivatives
57.45, with a varying extent of fusion. The oxidative
cycloaddition of perylene with 4-phenyl-1,2,4-triazoline-3,5dione, reported in 1974 by Zander, yielded the urazole
derivative 57.6, which was converted photochemically into
the fused 1,3-diazepine-2-one 57.7.301 The seven-membered
ring fused in the bay region of 57.7 is a rare feature, presumably
for steric reasons (other examples include a diazepine
hypericin hybrid 57.14302 and a hypocrellin B derivative
57.15303). Zanders bay-annulation approach was extended to
PDI derivatives 57.9ab by Langhals and Kirner.239 57.9a
shows a bathochromically shifted absorption at 600 nm, and
strong NIR uorescence with an emission maximum beyond
750 nm. In the same paper, the closure of a 1,2-dithiine ring in
the bay region of nitro PDI derivatives 57.10ab was achieved
by means of a reaction with elemental sulfur.239 57.11a is a
brilliant green, nonuorescent dye with signicantly lower
stability than other bay-annulated PDI systems.
In 2015, Zhang et al. reported the rst BN-annulated
perylene bisimide derivative 57.13.304 This compound was
obtained by reacting the 1-amino-PDI 57.12 with dichlorophenylborane. Compound 57.13 was explored as an OLED
material and as a selective anion sensor for uoride detection,
discriminating among 12 anions (F, Cl, Br, I, SO42, NO3,
CH3COO, H2PO4, CN, BF4, ClO4, PF6) in the
chloroform solution. The detection limit was as low as 1.5
M, and the observed eect was ascribed to N-deprotonation of
the azaborine ring.
In 2013, Jo and co-workers described an oxidative strategy
for the synthesis of graphene nanoribbons based on a perylene
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Scheme 57. [ghi]Heteroannulated Perylenoids Containing 6- and 7-Membered Ringsa
Reagents and conditions: (a)298 hydrazine hydrate, pyridine, reux, 30 min; (b)299 UV irradiation, MeOH; (c)3001,4-dioxo-1,2,3,4tetrahydrophthalazine, Pb(OAc)4, DCM, under nitrogen, 0 C, 3 h, then rt, 3 h; (d)301 4-phenyl-1,2,4-triazoline-3,5-dione, 3 h, rt with
simultaneous addition of Pb(OAc)4, then rt, 1 h, DCM, 59%, (e)301 h, mesitylene, under nitrogen, rt, 7 h, 24%; (f)239 4-phenyl-1,2,4-triazoline-3,5dione, chloranil, dry toluene, reux, 24 h, 25% for a, 25% for b; (g)239 sulfur, NMP, Ar, 130 C; (h)239 sulfur, DMF, Ar, 130 C, 10 h; (i)304
dichlorophenylborane, triethylamine, toluene, Ar, reux, 24 h.
Scheme 58. Nitrogen-Doped Graphene Nanoribbonsa
Reagents and conditions: (a)305 10 equiv of FeCl3, DCM/MeCN, 40 C, 3 days.
units.306 Compound C11.5, highly insoluble in common

solvents, could only be characterized by MALDITOF mass
spectrometry and was converted into a potassium salt for
further analysis. In subsequent work from the Xiao group, the
concept was extended to carbazole derivatives C11.67,
prepared by sunlight-induced intramolecular cyclization.108
C11.67 showed weak uorescence emission, each with a
maximum at ca. 640 nm, and enhanced nonlinear absorption in
comparison with the parent PDI.
A dierent approach was adopted in 2000 by Langhals and

Kirner, who obtained the perimidine-fused derivative 59.2 by
condensing the bay-fused anhydride 59.1 with peri-diaminonaphthalene.239 Compound 59.2 exhibits extended absorption
in the visible region but is nonuorescent. A tetrathiafulvalenefused PDI derivative 59.4 was similarly synthesized by Liu et al.
in 2010.307 Compound 59.4 is a -conjugated molecular dyad,
showing excited charge-transfer states at three dierent
oxidation levels, leading to intense optical absorption over a
wide spectral range.
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Chart 11. Bay-Fused PDI Derivatives106108,306
Scheme 59. Bay-Benzannulated PDI Systems with Extended Fusiona
Reagents and conditions: (a)239 1,8-diaminonaphthalene, diethylene glycol monomethyl ether, reux, 5 h, then 2 N HCl, rt, 16 h, 71%; (b)307 5,6diamino-2-(4,5-bis(propylthio)-1,3-dithio-2-ylidene)benzo[d]-1,3-dithiole, under Ar, propionic acid, 90 C, 2 h, then 135 C, 2 h, 65%.
Scheme 60. Synthesis of a Fan-Shaped Thiophene-Fused PAHa
Reagents and conditions:308 (a) (1) Sm, 1,2-diiodoethane, HMPA, THF, 1.5 h, rt, N2, (2) reactants in THF, 0 C, 20 min, then rt, 210 h; (b) pTsOH, benzene, reux, 512 h; (c) DDQ, toluene, reux, 718 h, overall yield (ac) 44%; (d) FeCl3, DCM, CH3NO2, rt, 5 h, 81%, or excess AlCl3,
anhydrous CuCl2 in CS2, air, 36 h, 91%.
a
intermediate was submitted to the oxidative annulation in the

presence of iron(III) chloride or by treatment with AlCl3/
CuCl2/O2.
A related fusion pattern was developed in 2002 by Fang and

co-workers, who reported on the synthesis of the fan-shaped
system 60.6 (Scheme 60).308 The synthesis consisted of a
SmI2-induced coupling reaction of ethyl thiophene-2-carboxylate (60.1) with -phenylacetophenone, followed by acidcatalyzed dehydration and DDQ oxidative cyclization, giving
tetraarylbenzothiophene 60.5 in a good overall yield. The latter
3.4. [cd]Heteroannulated Perylenoids
Perylene mono- and diimides (PMIs and PDIs) constitute the

largest class of [cd]heteroannulated perylenoids, and have been
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Scheme 61. Synthesis of Biscyclopenta-Fused Perylenoidsa
Reagents and conditions: (a)311 (1) KOH, 250 C, (2) O2; (b)312 t-BuOK, DBN, diglyme, 130 C for 1 h, then addition of 61.1, 130 C, 3 h, under
N2, then workup in air, 78%; (c)313 Ni(PPh3)2Br2, Zn, Et4NI, THF, 50 C, 20 h; (d)291 sulfur powder, N-methyl-2-pyrrolidone, 190 C, 3 h, 97%;
(e)316 on-surface dehydrogenation, Cu adatoms, annealing to 300 C.
by the codeposited or substrate-supplied transition metal

adatoms (Scheme 61). The dehydrogenation proceeded to
61.13 only in the presence of Cu adatoms and at elevated
temperatures. The formation of azo bridges led to characteristic
changes in the N 1s XPS signature and in NEXAFS spectra.
The dehydrogenated 61.13 formed porous networks with the
Cu adatoms with structures reecting the symmetry of the
underlying substrate.
Peropyrene (dibenzo[cd,lm]perylene) is an extended PAH
structure, which can be viewed (and synthesized317) as a union
of two phenalene subunits. 2,9-Diazaperopyrene 62.3 was rst
synthesized in 1989 by Helene, Lehn, et al. in the form of the
dimethyl dichloride salt 62.1 (Scheme 62).318 62.1 was
obtained by NBS aromatization of the diamine 62.2, which is
available from perylene dianhydride in two steps. 62.1 is
uorescent and was observed to dimerize in an aqueous buer
solution. 62.1 strongly binds to certain small aromatic
molecules, including nucleosides, and was investigated as a
potential selective uorescence probe and sequence-specic
articial nuclease.318 A dealkylating aromatization procedure for
62.2, developed by Stang et al., involved heating with a
palladium catalyst at high temperatures and furnished the Nunsubstituted 62.3.319 The low yield of the latter reaction was
apparently due to the low solubility of the product in common
solvents. Modied procedures for both nondealkylating and
dealkylating aromatizations were subsequently developed by
Wurthner and co-workers, enabling the synthesis of substituted
derivatives of 62.1 and 62.3.320,321 A fairly low-yielding but
remarkably simple synthesis of 62.3 was reported in 2009 by
Aksenov et al. as part of their research on naphthalene
acylation.322 The polycyclic framework was assembled in one
step from naphthalene and 1,3,5-triazine, which were heated
together in polyphosphoric acid (Scheme 62).
Stang et al. employed diazaperopyrene ligands to prepare
tetranuclear PtII- and PdII-based molecular squares 63.1ab
(Scheme 63).319 Each complex was prepared by reacting 62.3
with an equimolar amount of the square-planar cis-bis(phosphine) Pt or Pd bis(triate) complex. Compounds
63.1ab were more soluble than the free 62.3 ligand, but
intensely explored since the original synthesis of PDI by

Kardos.309 PDI and PMI derivatives fall outside the scope of
this Review unless they contain additional heteroatoms or fused
hetero rings. Accordingly, this section focuses on other types of
[cd]fused systems, notably on molecules containing vemembered rings and on N-doped peropyrenes.
In 1954, Bradley and Pexton reported a synthesis of the red
bisquinoxaline dye 61.2, which was obtained by oxidative
dimerization of acenaphtho[1,2-b]quinoxaline 61.1 (cf., section
6.2) under basic conditions (Scheme 61).310 A similar
dimerization was observed for aceanthra[1,2-b]quinoxaline
61.3. The resulting blue dye was identied as the trans
isomer 61.4 in a reinvestigation carried out in 1995 by Desilets
et al.311 A rened synthesis of 61.2 was reported in 2001 by
Sakamoto and Pac, who performed the oxidative coupling by
base-induced dimerization of 61.1, followed by aerial
oxidation.312 Both approaches could be applied to the synthesis
of a range of PDI-related systems.311,312 A conceptually related
strategy, based on a Ni-catalyzed reductive coupling, was
employed in 2003 by Ono et al. in the synthesis of the bispyrrole fused derivative 61.6.313 The compound showed red
uorescence with an emission maximum of ca. 570 nm.
The strategies used for the syntheses of [cd]heteroannulated
perylenoids include, in addition to dimerizations discussed
above, also ring contractions, exemplied by Langhals synthesis
of 61.7 lactams from the corresponding PDIs,314 as well as
direct heteroannulations. An example of the latter approach was
provided by Mullen and co-workers, who described a highly
selective reaction of 3,4,9,10-tetrabromo-1,6,7,12-tetrachloroperylene 61.8 with elemental sulfur, yielding bis-1,2-dithiole
61.9. The pink compound 61.9 showed an absorption
maximum at 560 nm in dichloromethane, which corresponded
to a bathochromic shift of 100 nm relative to 61.8.291 The
chlorine-free parent system of 61.9 was prepared by Scholl-type
dimerization of naphtho[1,8-cd][1,2]dithiole.315
In 2014, Shchyrba et al. described the on-surface reactivity of
4,9-diaminoperylene quinone-3,10-diimine 61.10.316 Compound 61.10 underwent a two-level dehydrogenation to
61.11 (1 H2) and 61.13 (3 H2), specically determined
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Scheme 62. Synthetic Routes to Diazaperopyrenesa
In 2001, Wurthner and co-workers reported a series of

diazadibenzoperylenes C13.1ad bearing mesogenic dodecyloxybenzoyl substituents.324 The aza coordination sites present
in these systems enabled additional control of dye packing by
intermolecular interactions, such as in the carboxylic acid
adducts C13.2ad (Chart 13). Compounds C13.1ad
exhibited strong luminescence in solution and in the solid
state, and were found to form thermotropic columnar liquid
crystalline phases with and without the addition of benzoic
acids. The formation of complex hydrogen-bonded superstructures between compounds C12.1ab and a substituted
isophthalic acid was also investigated.325 It was found that only
the phenoxy-substituted diazadibenzoperylene C12.1a formed
extended assemblies with a 1:1 stoichiometry (C13.3), whereas
for the C12.1b analogue, no indications of superstructure
formation were found. The dierent behavior was explained by
the presence of additional interactions, which were only
observed for C13.3, as revealed by concentration-dependent
optical absorption and uorescence spectroscopy. In 2006, the
rst, second, and third generation dendronized diazadibenzoperylenes C13.1eg were synthesized by DCC/DPTSactivated esterication of C12.1c with the respective benzoic
acid dendrons.326 The yields of diazadibenzoperylene dendrimers C13.1eg successively decreased from the rst to the
third generation (75% to 20%), in line with the increasing steric
hindrance of the four dendritic wedges around the core. The
rst and second generation dendrimers aorded Ag-linked
coordination polymers, while the third generation resisted
polymerization, apparently as a result of the steric shielding of
the aza coordination sites by dendritic wedges.
The unsubstituted 1,3,8,10-tetraazaperopyrene (TAPP) 64.1
was rst prepared in 2007 by Gade and co-workers in a reaction
of 4,9-diamino-3,10-perylenequinone diimine 61.9 with triethyl
orthoformate (Scheme 64).327 2,9-Disubstituted derivatives
64.2ag were similarly obtained by reacting 61.9 with the
corresponding carboxylic acid chlorides or anhydrides. A range
of aryl-disubstituted TAPPs was subsequently synthesized using
the same general method.328 Compounds 64.1 and 64.2a
exhibit low solubility in common organic solvents due to
ecient aromatic stacking between peropyrene cores.327 The
UVvisible absorption spectra of TAPPs contain a characteristic visible * absorption band at 440 nm with a strong
vibrational progression ( 1450 cm1). This absorption
Reagents and conditions: (a)318 (1) NBS, AcOH, reux, 30 min, (2)
ion exchange resin; (b)319 neat, 10% Pd/C, 300310 C, 1 h; (c)322
PPA, 6570 C, 3 h, then 100110 C, 6 h.
their complete purication and characterization was not feasible

due to their low solubility in common organic solvents. The
Wurthner group employed tetraaryloxy-substituted diazaperopyrene bridging ligands in the transition metal-directed selfassembly with Pd(II) and Pt(II) phosphane triates, which
resulted in complex dynamic equilibria between molecular
triangles 63.2ad and molecular squares 63.3ad in
solution.323 It was found that the equilibria depended on
several factors, such as the metal ion (platinum complexes
exhibited higher stability than their Pd analogues) or the
solvent. The introduction of bulky p-(tert-butyl)phenoxy
groups as the R 1 substituents shifted the equilibrium
signicantly in the direction of the molecular squares.
The suitability of the diazaperopyrene derivative C12.1a as a
photo- and redox active supramolecular building block was
investigated by Wurthner and co-workers, who performed
complexation experiments with carboxylic acids (3,4,5trisdodecyloxy benzoic acid) and a range of metal ion sources:
(trans-[Pd(PPh3)2(OTf)2]), AgOTf, and ZnTPP, leading to
structurally diverse adducts, C12.3, C12.4, and C12.5ab
(Chart 12).320,321 Compounds C12.1a and C12.2 were
characterized by optical absorption and uorescence spectroscopy,321 exhibiting emission quantum yields of 75% and 50%,
respectively. The C12.2 dication revealed reversible oxidation
and reduction waves, whereas the oxidation of C12.1ab
underwent irreversible deposition of a conductive lm on the
electrode surface.
Scheme 63. Metallacycles with Diazadibenzoperylene Bridging Ligands319,323
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Chart 12. Tetraaryloxy-Substituted Diazadibenzoperylenes320,321
Chart 13. Diazadibenzoperylenes Bearing Mesogenic Substituents324326
TAPPs can be halogenated on the perylene core, yielding

tetrachloro332 and tetrabromo333 derivatives (64.5 and 64.6,
respectively), when reacted under highly acidic conditions with
either dichloroisocyanuric acid (DIC) or dibromine. Halogen
substitution has a drastic inuence on the optical and
electrochemical properties of TAPPs. Members of the 64.5
series are strongly uorescent and yield high-performance nchannel transistors with a eld-eect mobility of up to 0.14 cm2
V1 s1, an on/o current ratio of >106, and good long-term
stabilities. Currentvoltage characteristics of the TFTs based
on the bromo derivatives 64.6 established electron mobilities of
up to n = 0.032 cm2 V1 s1. Halogenated TAPPs were
subjected to further functionalization using metal-catalyzed
coupling reactions and nucleophilic halogen substitutions to
yield a range of aryl-,334,335 alkynyl-,334 and aryloxysubstituted335 derivatives. Water-soluble, pyridinium-containing
TAPP derivatives showed both high photostability and high
uorescence quantum yields (>80%) in aqueous solutions.335
exhibits a bathochromic shift upon protonation of the nitrogen

atoms. The rst and second as well as the third and fourth
protonations occur concomitantly, which implies that the pKa
values are very similar within each pair. TAPP derivatives
undergo two electrochemically reversible one-electron reductions. In toluene solutions, TAPP dyes show weak uorescence
( 0.02), which typically becomes much more intense upon
protonation ( = 0.47 for 64.1 in TFA).
64.1 contains four potentially metal-ligating exodentate
nitrogen donors. Furthermore, the CH bond between each
two nitrogen atoms oers the potential of tautomerization to an
N-heterocyclic carbene isomer or may undergo metal-induced
CH activation at elevated temperatures. This last property
was exploited in a study of TAPP metalorganic coordination
networks self-assembled on the Cu(111) surface.329331 Upon
annealing at 250 C, the initially formed Cu-coordinated 2D
network was converted into covalently linked oligomer chains,
for which the general structure 64.3 was proposed on the basis
of STM data.
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Scheme 64. Synthesis of 1,3,8,10-Tetraazaperopyrenesa
Reagents and conditions: (a)327 triethyl orthoformate, cat. formic acid, reux, 48 h; (b)332 dichloroisocyanuric acid, concentrated H2SO4, 85 C, 72
h, 4487%; (c)333 Br2, I2 (cat.), fuming H2SO4, 80 C, 10 h, 2981%.
Scheme 65. Extended [cd]-Fused Rylene Dyesa
Reagents and conditions: (a)336 BINAP, Pd2(dba)3, NaOtBu, toluene, 80 C, overnight; (b)336 K2CO3, ethanolamine, 130 C, 5 d (for 65.5);
NaOtBu, DBN, diglyme, 130 C, 16 h (for 65.6); (c)136 Zn(OAc)2, quinoline, 180200 C; (d)136 imidazole, 140 C.
2-acetylaniline as the nucleophilic component.136 The condensation performed on perylene anhydrides 65.8 and 65.11
showed remarkable chemoselectivity dependent on reaction
conditions. Heating in quinoline in the presence of catalytic
zinc acetate produced 4-oxoquinoline products 65.7 and 65.10.
When the reaction was carried out in imidazole, the
imidizationaldol condensation sequence was followed by a
rearrangement step, which produced the thermodynamically
more stable 4-hydroxyquinoline products 65.9 and 65.12.
65.9 and 65.12 can be viewed as remotely [cd]heteroannulated perylenoids because the hetero ring is not
directly fused to the perylene substructure. Such systems are
relatively rare, with two additional examples provided by
heterofused isoviolanthrone dyes (Chart 14). Cyananthrene
C14.1, reported in 1952 by Bradley and Sutclie, was obtained
by fusing 13H-phenaleno[2,1-f ]quinolin-13-one with potassi-
These dyes showed selective staining of cell nuclei and low

cytotoxicity with IC50 values of up to 67 M.
Extended rylene dyes 65.56, bearing a structural resemblance to Indanthrene Olive Green B (C22.2, section 4.2),
were reported in 2002 by Mullen and co-workers.336 The
synthesis involved a Buchwald-type double amination between
1,5-diaminoanthraquinone and each of the imides 65.12,
followed by base-promoted cyclization of the intermediate
oligomers 65.34. Dyes 65.56 showed extended chargetransfer absorptions in the NIR range (up to ca. 900 and 1400
nm, respectively), as well as excellent photostability. The NH
groups in 65.56 are stabilized by intramolecular hydrogen
bonding, leading to negligible solvatochromism.
The tandem condensation method of Mullen et al., used for
the construction of the 3a1-azaperylene substructure (Scheme
30, section 3.1), was also employed in a simpler version, using
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Chart 14. Hetero-Fused Isoviolanthrone Dyes337,338
intramolecular cyclization of a bis-anthraquinone precursor

carried out in the presence of Cu and H2SO4.341 Propellershaped indole-fused PDI derivatives 66.6ab were obtained by
Wang, Jiang, et al. in a 4-fold Heck-type arylation reaction.342
These systems showed reduced HOMOLUMO gaps, and
intense absorption in the 500750 nm range. Pyrrole ring
fusion in hypocrellin derivatives was reported by Zhang and coworkers.343,344 Their method involved heating hypocrellin B
(67.1) with appropriate amines in pyridine, yielding fused
systems 67.2ad, characterized by enhanced optical absorption
relative to the parent system (Scheme 67).
Scheme 67. Synthesis of Amino-Bridged Hypocrellin Ba
um hydroxide and potassium acetate.337 In 1966, Nair and Shah

proposed the structure C14.2 for a dye obtained by AlCl3catalyzed cyclization of a disubstituted isoviolanthrone
precursor.338
3.5. ortho-Heteroannulated Perylenoids
Early examples of ortho-heterofused perylene derivatives, such

as 66.1, date back to the work of Zinke and co-workers
(Scheme 66).339 In 1934, they reported the synthesis of the bisquinoxalino system 66.3 in an acid-catalyzed condensation of
2,11-dihydroxyperylene-3,10-dione 66.2 with ortho-phenylenediamine.340 A structurally related indole-fused helianthrone
derivative 66.4 was obtained in 1970 by Wick, as a product of
a
Reagents and conditions: (a)344 amine, pyridine, darkness, 1020 h,
50 C.
In 2012, an imidazole-[a]fused PDI derivative 68.2 was

described by Langhals and Hofer (Scheme 68).345 68.2,
obtained by reacting PDI with sodium amide and benzonitrile,
was subjected to a sequence of transformations leading
ultimately to the bisperylene dyad 68.6. Heterodimer 68.7
was similarly assembled using the Suzuki coupling reaction.
These two strongly absorbing dyes were characterized by
dynamic reorganization of the biaryl torsional angle in the
excited state, which led to considerably increased Stokes shifts.
In 2013 Pei, Wang, et al. prepared an extended fused system
69.2, containing both perylene and pyrene substructures
(Scheme 69).346 The four ortho-fused thiophene rings were
installed by performing a quadruple Scholl-type cyclization on
the substituted pyrene precursor 69.1. 69.2 was the rst
example of a pyrene derivative fused outside the K-regions and
was described as a thiophene-fused superpyrene. In
concentrated solutions, 69.2 was observed to undergo Haggregation, as evidenced by UVvis spectroscopy, a feature
that might be benecial for charge transport in condensed
phases. The self-assembly of 69.2 was investigated by SEM and
TEM measurements, which revealed the formation of 1D
nanowires with high aspect ratios.
Scheme 66. Bis-ortho-Fused Perylenoidsa
4. PYRENOIDS
Both the parent hydrocarbon pyrene and its numerous
derivatives are currently of great importance as aromatic
building blocks for use in device applications.347 A variety of
fused heterocyclic systems containing pyrenoid substructures
were originally developed by the dyestu industry. The most
important of these derivatives, usually acridine and anthraquinone dyes, are highlighted in the following sections. For
comprehensive reviews, the reader is referred to chapters by
Tilak and Ayyangar,348 Venkataraman and Iyer,349 Hunger and
Herbst,350 and to the book by Allen.1 This section focuses on
heteroatom-containing pyrenoids containing at least ve fused
rings, although relevant nonfused (four-ring) heterapyrenes are
Reagents and conditions: (a)340 o-phenylenediamine, nitrobenzene,

glacial AcOH, reux; (b)342 [Pd2(dba)3], P(t-Bu)3, K3PO4, 1,4dioxane, reux, argon.
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Scheme 68. Synthesis of Imidazole[e]-Fused Perylene Derivativesa
Reagents and conditions:345 (a) sodium amide, benzonitrile; (b) KOH, tert-butyl alcohol; (c) Cu, 3-picoline, 48%; (d) Br2, chloroform, 88%; (e)
Pd(OAc)2, (C4H9)4NBr, NEt3, toluene, 60%.
Scheme 69. Synthesis of a Thiophene-Fused Superpyrenea
Chart 15. Classication of Pyrenoids Used in This Sectiona
a
Reagents and conditions: (a)346 FeCl3, CH3NO2, DCM, N2 atm, 8
min, 0 C.
also discussed. The material is grouped into seven sections

(Chart 15). Section 4.1 discusses the rich chemistry of
heteratriangulene derivatives (for a recent account, see a review
by Lacour et al.32). In sections 4.2 and 4.3, we summarize the
chemistry of the remaining heterapyrenes. In particular, BN
containing pyrenes are discussed along with other aza systems
in section 4.2 (for a B-only pyrenoid system, 39.6, see Scheme
39, section 3.1). The peri- and ortho-heteroannulated pyrenes
are discussed in sections 4.4, 4.5, and 4.6. The chemistry of
pyrazacenes, recently reviewed by Mateo-Alonso,351 is a major
topic in section 4.6. As in the preceding sections, the presence
of a cyclic imide or anhydride functionality does not count
toward the required number of rings and peri-fusion points.
Horizontally expanded NDI derivatives, containing additional
rings ortho-fused to the naphthalene fragment, such as the
systems recently reported by the groups of Gao, 352
Takimiya,353 and Wurthner,354 are accordingly not covered
here. Such derivatives, which are of high interest as organic
semiconductors, have been reviewed recently by Suraru and
Wurthner50 and by Zhang et al.355

indicated.
a
shell molecule with a triplet ground state, the majority of

existing heteratriangulenes have closed-shell congurations,
which are achieved through appropriate placement of
heteroatoms, exocyclic double bonds, and saturation points.
In particular, a large number of azatriangulenes have been
synthesized, containing the triply bridged, electron-decient
triphenylamine core. The rst such system, 70.3, possessing
three carbonyl bridges, was reported by Hellwinkel and Melan
in 1971.357 It was originally obtained by heating trimethyl
2,2,2-tribenzoate 70.2 in the presence of either sulfuric or
phosphoric acid. An improved procedure, reported by Field and
Venkataraman, furnished 70.3 in 80% yield.358 70.3 is a planar
molecule with D3h symmetry, yielding dense packing in the
solid state (Kitaigorodskii packing coecient = 0.72), with
columnar -stacks being formed along the a-axis. The
absorption maximum of 70.3 was observed at 422 nm (10%
triuoroacetic acid in dichloromethane), with the corresponding green uorescence at 499 nm. The solubility of 70.3 in
4.1. Triangulenes
Triangulene (70.1, Scheme 70), the simplest non-Kekule PAH

system,356 forms the structural basis of numerous heterocyclic
analogues. In contrast to triangulene itself, which is an openBA
Chemical Reviews
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Scheme 70. Synthetic Routes to Carbonyl-Bridged Azatriangulenesa
a
Reagents and conditions: (a)357 MeOH, H2SO4, 24 h, 100105 C; (b) H3PO4, 1620 h, 180 C; (c)358 (1) NaOH, EtOH:water (1:1), 3 h, reux,
(2) HCl to pH 23, (3) SOCl2, DMF (cat.), dry DCM, 3 h, reux, (4) SnCl4, reux, 15 h, (5) NaOH, 0.5 h; (d)359 I2, Ag2SO4, EtOH, 12 h, rt; (e)
(1) KOH, MeOH, water, overnight, 50 C, (2) cooled, water, HCl to pH = 3, (3) SOCl2, DMF (cat.), dry DCM, 3 h, reux, (4) SnCl4, reux, 24 h,
(5) NaOH, 1 h.
Chart 16. Carbonyl-Bridged Azatriangulenes
carbazole branches and the heteratriangulene core. The organic

light-emitting diodes (OLEDs), fabricated with C16.1 and
C16.2 as nondoping emitters, exhibited aggregation-induced
luminescence, peaking at 600 and 630 nm, respectively. A
maximum luminance of 1586 cd m2 at current eciency of 5.3
cd A1 was measured for C16.1, whereas C16.2 yielded 827 cd
m2 at a current eciency of 6.9 cd A1.
In the same year, Chen et al. described the synthesis of
C16.3a by a palladium-catalyzed Sonogashira cross-coupling
common organic solvents was too low to permit electrochemical measurements.

In 2009, Du, Chen, and co-workers used direct iodination of
70.2 to obtain the triiodo derivative 70.5 (Scheme 70).359
Compound 70.5, a versatile synthetic intermediate, was
converted into two star-shaped donoracceptor dendrimers
C16.1 and C16.2 using Ullmann coupling.359 Both dendrimers
showed good thermal stabilities and distinct ground-state
intramolecular charge transfer (ICT) transitions between
BB
Chemical Reviews
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Scheme 71. Synthesis of Arylvinylidene-Bridged Heteratriangulenesa
Reagents and conditions: (a)366 CBr4, PPh3, toluene, 18 h, 110 C; (b) phenylboronic acid or 2-naphthylboronic acid, Pd(PPh3)4, K2CO3, water,
toluene, dimethoxyethane, 36 h, 100 C; (c) FeCl3, CH3NO2, DCM, 30 min, 0 C; (d) FeCl3, CH3NO2, DCM, air, 18 h, rt; (e)367 (1) Lawessons
reagent, dry toluene, 10 min, rt, (2) 11.5 h, 90 C; (f) (1) 9-diazo-9H-thioxanthene, dry THF, dry toluene, 1.5 h, 0 C, (2) PPh3, dry xylene, 21 h,
135 C; (g) (1) diphenyldiazomethane, dry THF, 2 h, rt, (2) PPh3, dry xylene, 16 h, 135 C; (h) H2O2 (30 wt %), glacial AcOH, 3 days, rt.
reaction between 70.5 and 1-dodecyl-4-ethynylbenzene.360

Two-level self-assembly of C16.3a, from nanowires to microrods, was observed when the dichloromethane solution of
C16.3a was mixed with methanol. This type of self-assembly
was attributed to the strong stacking interactions of
heteratriangulene cores and the hydrophobic interactions of
alkyl chains with solvent molecules. The same behavior was
later observed for derivatives with shorter alkoxy chains (hexyl,
octyl, and decyl).361
In 2011 Pisula, Mullen, et al. used the alkyl-substituted
C16.4a, which is soluble in common organic solvents, to
fabricate bers characterized by very good long-range alignment.362 The bers were prepared via simple dip-coating, by
controlling the concentration of C16.4a. In the ber, columnar
stacks of molecules were oriented along the main axis, with one
crystal plane within the ber arranged preferentially in-plane to
the substrate surface. Two years later, Kivala, Mullen, et al.
synthesized a series of carbonyl-bridged heteratriangulenes with
n-dodecyl chains attached through dierent spacers to the
nitrogen-centered core.363 All compounds were obtained from
70.5 using dierent cross-coupling reactions. All ethynylated
derivatives C16.3bf were prepared in good yields by the
Sonogashira reaction with the corresponding terminal
alkyne.363,364 Compound C16.4a was prepared by the Pdcatalyzed Negishi reaction with n-dodecylzinc bromide, whereas
C16.4b was obtained by using SuzukiMiyaura coupling with
4-dodecylphenylboronic acid. The self-assembly behavior of
these derivatives was investigated in solution, on surface, and in
the bulk. It was found that additional phenylene moieties
between the core and alkyl chains facilitated self-assembly by
extending the -conjugated polycyclic disc. The rod-like
ethynylene spacers introduced additional exibility, thus
lowering the overall aggregation tendency. The combination
of both features in the phenyleneethylene moieties was found

to induce thermotropic liquid crystallinity.
In 2014, multichromophoric carbonyl-bridged triarylamines
were obtained by Hildner, Kivala, Schmidt, and co-workers.365
Naphthalimides C16.6 and C16.7 as well as the reference
system C16.5 were prepared from an appropriate triamine
derivative of 70.4 (Chart 16). Steady-state and time-resolved
spectroscopy of C16.67 provided clear evidence for energy
transfer in both multichromophoric compounds. In compound
C16.6, the energy was forwarded from the peripheral
naphthalimides to the carbonyl-bridged triarylamine core,
while in compound C16.7 the same process proceeded in the
opposite direction. Compound C16.7 is an ecient gelator for
ortho-dichlorobenzene (at 0.7 mM concentration) and retained
its energy-transfer and photoluminescent properties in the gel
state.
A strategy for expanding heteratriangulenes at the bridging
positions was developed in 2014 by Yamaguchi and co-workers
(Scheme 71).366 In the rst step, compound 71.1a was
converted into the hexabrominated derivative 71.2, which was
further transformed by the SuzukiMiyaura coupling with
phenylboronic acid or 2-naphthylboronic acid into the
corresponding 6-fold coupling products 71.3ab. 71.3a then
underwent partial oxidative coupling to yield the 10-ring-fused
product 71.4. When the reaction was conducted in the
presence of air, a dicarbonyl-substituted species 71.5 was
obtained, resulting from the cleavage of two exocyclic double
bonds. The dehydrogenative coupling of 71.3b smoothly took
place at the naphthyl groups, to produce the dibenzo[c,g]uorenylidene-substituted 71.6. Compound 71.6 has a highly
twisted conformation due to the overcrowded alkene moieties,
which impart a highly electron-accepting character to the
naturally electron-rich heteratriangulene skeleton, thereby
BC
Chemical Reviews
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Scheme 72. Synthesis of Dimethylmethylene-Bridged Heteratriangulenesa
Reagents and conditions: (a)368 85% H3PO4, 0.5 h, rt; (b)369 (1) 85% H3PO4, 2 h, rt, (2) 2 M NaOH; (c)371 (1) POCl3, dry DMF, Ar atm, 0 C,
(2) 0.5 h, rt, (3) 15 h, 80 C; (d) (1) PH3PCH3I, n-BuLi, anhydrous ether, 78 C, (2) 1 h, rt, (3) 72.3a, 15 h, rt; (e) KI, KIO3, AcOH, 2 h, 80 C;
(f) (1) NBS, chloroform, 30 min, 0 C, (2) 1 h, rt; (g) (1) 72.4a, K2CO3, n-Bu4NBr, DMF, water, Ar atm, 20 min, (2) Ph3P, 72.5a, 15 min, rt, (3)
Pd(AcO)2, 15 h, 100 C; (h) (1) n-BuLi in hexane, THF, Ar atm, 15 min, 78 C, (2) 1 h, rt, (3) 2-isopropoxy-4,4,5,5-tetramethyl[1,3,2]dioxaborolane, 16 h, rt; (i) Pd(PPh3)4, Na2CO3, toluene, water, Ar atm, 30 h, 110 C.
a
Dimethylmethylene-bridged triarylamines are formally azatriangulene derivatives lacking the complete -conjugation in
the peri-fused framework. They will be discussed here because
the synthetic methodology involved in their chemistry is of
direct relevance to the synthesis of fully -conjugated
heteratriangulenes. The rst dimethylmethylene species,
72.2a, was synthesized by Hellwinkel and Melan in 1974 by
acid-catalyzed cyclization of the tricarbinol 72.1a (Scheme
72).368 Using 72.2a as the building block, Lai, Samoc, and coworkers developed star-shaped and dendritic acetylene-linked
oligomers, such as C17.1a (Chart 17).369 Those compounds
combined high uorescence quantum yields with large twophoton absorption cross sections (13006100 GM). Bromosubstituted (C17.1b) and cationic (C17.1c) tetramers were
obtained in the same year by Lai, Liu, and co-workers, using a
similar synthetic strategy, showing TPA cross sections of 4340
GM (in toluene) and 4150 GM (in methanol), respectively.370
The approach developed by Lai et al. is illustrated by the
synthesis of two starburst molecules with dimethylmethylenebridged triangulene moieties that are connected either directly
(as in 72.10) or by vinylene links (72.7).371 The unsymmetrical
substitution needed for the assembly was achieved either by
preparing unsymmetrical arylamine precursors and their
inducing NIR absorptions and multiredox behavior with a low

reduction potential.
An alternative approach to vinylidene-bridged azatriangulenes was proposed in 2015 by Kivala et al.367 Instead of the
dibromoolenation/Suzuki-coupling sequence of Yamaguchi et
al., they employed the BartonKellogg olenation as the key
bond-forming step (Scheme 71). Initially, azatriangulenes
71.1bc were converted into thioketones 71.7bc with
Lawessons reagent and subjected to the 3-fold olenation
with either diphenyldiazomethane or 9-diazo-9H-thioxanthane.
The intermediate thioepoxides were used directly without
purication for the subsequent reaction with triphenylphosphine because of their tendency to decompose during column
chromatography. To investigate the eect of the electronwithdrawing sulfone units on the optoelectronic properties of
the -system, compound 71.8b was oxidized in the presence of
H2O2 and acetic acid. Further attempts to cyclize compounds
71.8bc and 71.9bc using chemical or photochemical
oxidation led to material decomposition or complex mixtures
of unidentiable products. 71.8bc and 71.9bc are fairly
strong electron donors, susceptible to several reversible
oxidation steps. In particular, compound 71.8b undergoes the
rst oxidation at almost the same potential as ferrocene.
BD
Chemical Reviews
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Chart 17. Dimethylmethylene-Bridged Azatriangulenes369,370,372,374,375
making the system a good candidate for a spin-selective

conductor. The half-metallicity was robust under external strain
beyond the eect of a substrate. In 2013, Fasel and Mullen
reported a comparative analysis of solution and surfacemediated syntheses of heteratriangulene macrocycles.374 Both
synthethic methods started from the same precursor, a
dibromo-substituted dimethylmethylene triphenylamine. The
preference for macrocyclization (C17.4a) over the formation of
the zigzag oligomers (C17.3) was revealed on surface as a result
of two-dimensional connement. Using solution chemistry, the
C17.4a macrocycle was obtained on a several hundredmilligram scale and characterized by single-crystal X-ray
analysis. C17.4a was brominated and subjected to the
SuzukiMiyaura cross-coupling to yield the more extended
systems, C17.4b and C17.4c. In comparison to 72.2a,
compounds C17.4ac showed a deep blue emission in
solution, together with a signicant improvement in the
photoluminescence quantum yield. These eects resulted
from the extended -conjugation along the cyclic backbone.
C17.2, an air-stable, p-type semiconductor polymer, was
synthesized in 2013 by List, Mullen, and co-workers and
employed for the construction of air-stable OFET devices.375
subsequent derivatization (e.g., 72.1b) or by selective

monosubstitution of 72.2a, the latter leading to the vinyl
derivative 72.4a. Trihalogenation of 72.2a was achieved using
either the KI/KIO3 mixture or the NBS. The vinylene target
72.7a was obtained from 72.4a and 72.5 using the Heck
reaction conditions, whereas the directly linked 72.10b was
prepared by means of the SuzukiMiyaura coupling between
72.9b and 72.6. Both starburst molecules showed decreased
oxidation potentials, resulting from the increased HOMO
energy level. Double-layer sandwich electroluminescence
devices were fabricated from both oligomers. Compound
72.10b showed signicantly enhanced performance in comparison with 72.7a.
In 2011, Fasel and co-workers reported the assembly of
tribromo-substituted 72.6 on the Ag(111) surface.372 Depending on the activation temperature, two-dimensional porous
metal-coordination or covalent networks were obtained,
structurally similar to the C17.4 motif. One year later, Kan,
Deng, Yang, and co-workers presented rst-principles calculations demonstrating that the porous sheet obtained by Fasel
et al. is a ferromagnetic half-metal.373 The computed band gap
in the semiconducting channel was found to be roughly 1 eV,
BE
Chemical Reviews
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Scheme 73. Synthesis of Thiophene-Functionalized Azatriangulenesa
Reagents and conditions: (a)376 Pd(PPh3)4, K2CO3, THF, water, 18 h, reux; (b) TFA, THF, water, 6 h, rt; (c) cyanoacetic acid, MeCN,
chloroform, piperidine, 6 h, reux.
of 0.745 V, and a ll factor of 0.70, corresponding to an overall

conversion eciency of 8.71%. The triply substituted system
73.6, also reported by Ko et al., exhibited good p-type
semiconducting performance in solution-processed OFETs.378
A power conversion eciency of 4.16% was observed, with a
hole mobility and on/o ratio of 7.6 103 cm2 V1 s1. In
2013, Grat zel, Liu, and co-workers showed that the
introduction of an alkene linkage between the triangulane
core and the peripheral group in 73.7 and 73.8 improved
electron delocalization and caused a large red shift of the
absorption peaks.379 The power conversion eciency for
compounds 73.7 and 73.8 was 7.51% and 8.00%, respectively.
In 2012, Perry, Mullen, and co-workers reported a study of
the one- and two-photon absorption properties of azatriangulenes with one, two, or three diarylborane arms (74.2ac,
Scheme 74).380 Compounds 74.2ac were obtained from one-,
two-, or tribrominated dimethylmethylene bridged azatriangulenes 74.1ac, in reaction with n-BuLi followed by addition of
Mes2BF. These compounds were stable at ambient conditions
because of the presence of two mesityl groups at each boron
center, and their solubility increased with the increasing
number of B-moieties. It was found that, on going from the
single-arm to the two- and three-arm systems, the peak in twophoton absorption (TPA) cross-section was suppressed by
factors of 311 for the lowest excitonic level associated with
the electronic coupling of the arms, whereas it was enhanced by
factors of 48 for the higher excitonic level. These results
showed that the coupling of arms redistributed the TPA crosssection between the excitonic levels in a manner that strongly
Because of the deeper-lying HOMO level (EHOMO = 5.1 eV)

and wider bandgap (Eg = 2.9 eV) of C17.2, bottom-gate/
bottom-contact FETs could be fabricated, characterized, and
stored under ambient conditions, showing excellent stability
over months. The optimization of electrode/ and dielectric/
polymer interfaces yielded mobilities of 4 103 cm2 V1 s1
and on/o current ratios of 105, showing that C17.2 is a
viable alternative for the best performing amorphous air-stable
semiconducting polymers. Polymer C17.2 underwent Nprotonation by hydrochloric acid in chloroform solutions,
resulting in signicant changes of the OFET characteristics.
In 2011, Ko and co-workers developed a series of thiophenefunctionalized azatriangulenes for use as sensitizers in dyesensitized solar cells (73.4a and 73.5ab, Scheme 73).376 The
synthesis of 73.4a (Scheme 73) involved stepwise elaboration
of the oligomer chain using the SuzukiMiyaura coupling
reaction and Knoevenagel condensation, and a similar approach
was employed for the preparation of other derivatives. Under
standard AM 1.5 sunlight, the sensitizer 73.5b yielded a shortcircuit photocurrent density of 15.32 mA cm2, corresponding
to an overall conversion eciency of 7.86%. The 73.5b cell
exhibited excellent stability, revealing only a slight change after
1000 h of light soaking at 60 C. The cell showed a higher
open-circuit voltage (Voc) as compared to that of 73.5a due to
an increased electron lifetime (C) in the conduction band of
TiO 2 . Further work from the Ko group focused on
azatriangulene derivatives 73.4bd.377 Under standard global
air mass 1.5 solar conditions, the 73.4d cell gave a short circuit
photocurrent density of 16.78 mA cm2, an open-circuit voltage
BF
Chemical Reviews
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Azatriangulene derivatives containing oligouorene arms,

75.6ac, were obtained in 2012 by Yang, Wu, and coworkers.383 These materials showed glass transitions in the
123129 C range and a good lm-forming ability. Doublelayer OLEDs fabricated from 75.6ac showed high electroluminescence performance. In particular, the device based on
75.6c achieved a maximum current eciency of 3.83 cd A1
and a maximum external quantum eciency of 4.19% with CIE
coordinates of (0.16, 0.09).
C18.1, the radical cation of dimethylmethylene-bridged
heteratriangulene, a rare example of a stable triphenylamine
radical cation without para-substitution, was obtained in 1975
by Bamberger, Hellwinkel, and Neugebauer (Chart 18).384 It
was generated by oxidizing the parent 72.2a with lead
tetraacetate in triuoroacetic acid and characterized using
ESR spectroscopy. In 2013, Wang and co-workers succeeded in
obtaining the C18.1 radical cation in nonacidic solvents, using
either Ag[Al(OC(CF3)3)4] or B(C6F5)3 as the oxidant.385
Additionally, it was shown that the reaction of C18.1 and its
parent amine with trace amounts of Ag+ led to the formation of
the dimeric C18.2a dication. The X-ray structural analysis and
theoretical calculations indicated a signicant singlet biradicaloid contribution (C18.2b), structurally analogous to Chichibabins hydrocarbon.
In 2005, Okada and co-workers reported a new tetraheteratriangulene system, 2,2:6,2:6,6-trioxytriphenylamine 76.7
(Scheme 76).386 Compound 76.7 was obtained from 2,6diuoro-nitrobenzene 76.1 in a six-step sequence, involving
nucleophilic substitutions and BuchwaldHartwig aminations
as the key bond-forming steps. The chemical oxidation of 76.7
to the stable, planar radical cation salt 76.8a was performed by
using tris(p-bromophenyl)aminium hexauorophosphate. In
contrast to the radical cation, the neutral form 76.7 had a
shallow bowl structure in the solid state. In 2007 Shiomi,
Okada, et al. described the solid-state structures and magnetic
properties of the tetrachloroferrate (76.8b) and tetrachlorogallate (76.8c) radical cation salts of 76.7.387 In the 76.8b
crystals, the radical cations form -stacked dimers surrounded
by tetrachloroferrate anions, which also form dimers in the
solid state. The magnetic properties of 76.8b were characterized by strong (2 J/kB = 1.3 103 K, H = 2JS1/2S1/2)
and weak (2 J/k B = 1.76 K, H = 2JS 5/2 S 5/2 )
antiferromagnetic interactions due, respectively, to the radical
cation and [FeCl4] dimers. In 2012, Okada et al. reported a
Scheme 74. Synthesis of Azatriangulenes with One, Two, or

Three Diarylboryl Acceptorsa
a
Reagents and conditions: (a)380 (1) n-BuLi, 20 min, 78 C, (2)
Mes2BF, 78 C, (3) overnight, rt.
favored the higher-energy excitonic level. The data analysis

revealed that, in compound 74.2b, a sizable increase in peak
TPA cross-section for the lowest excitonic level was observed,
whereas for compound 74.2c, the corresponding peak was
weakened and shifted to lower energy.
The diarylmethylene-bridged azatriangulene 75.2 (Scheme
75), reported in 2009 by Ma et al., possessed an almost planar
skeleton and exhibited excellent thermal and morphological
stability.381 Phosphorescent OLED devices with 75.2 as the
host material and Ir(ppy)3 as the triplet emitter showed a
maximum current eciency of 83.5 cd/A and a maximum
power eciency of 71.4 Im/W for green electrophosphorescence. Extended derivatives 75.4 and 75.5, obtained from
75.2 using triple electrophilic bromination and Suzuki coupling,
exhibited excellent thermal stabilities with high glass transition
temperatures of 237 and 272 C, respectively, as well as good
solution-processability. 75.4 and 75.5 additionally displayed
good hole mobility, combined with ecient hole injection and
electron-blocking functions.382 Compound 75.4 showed
signicantly red-shifted absorption and emission, reecting
the reduced band gap in comparison to 75.5. Double-layer
Alq3-emitting OLEDs with 75.5 as the transporter layer showed
greatly improved performance relative to standard NPB-based
devices prepared by vacuum evaporation. The optimized threelayer Alq3-emitting OLEDs, using 75.5 and NPB as a double
hole transport layers, exhibited the maximum current eciency
of 6.83 cd/A.
Scheme 75. Synthesis of Diarylmethylene-Bridged Azatriangulenesa
Reagents and conditions: (a)381 (1) 4-bromotoluene, n-BuLi, 10 C, (2) overnight, rt, (3) HCl, AcOH, 3 h, reux; (b)382 (1) NBS, chloroform, 0
C, (2) 12 h, rt; (c) Pd(PPh3)4, Na2CO3, toluene, water, 36 h, 90 C; (d)383 Pd(PPh3)4, 2 M Na2CO3, THF, water, 48 h, reux.
a
BG
Chemical Reviews
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Chart 18. Azatriangulene Radicals385
Scheme 76. Synthesis of Trioxytriphenylamine and Its Derivativesa
a
Reagents and conditions: (a)386 (1) 2-bromo-3-methyoxyphenol, NaH, dimethylsulfoxide, 1 h, 6570 C, (2) 2,6-diuoronitrobenzene, 2.5 h, 130
C; (b) (1) 2-bromo-3-uorophenol, NaH, dimethylsulfoxide, 1 h, 6570 C, (2) 76.2, 3 h, 130 C; (c) hydrazine hydrate, Pd/C, p-bromophenol,
EtOH, 2 h, reux; (d) NaO-t-Bu, Pd(dba)2, P(t-Bu)3, toluene, 3 h, reux; (e) (1) BBr3, DCM, 78 C to rt; (f) K2CO3, DMF, overnight, rt; (g)
tris(p-bromophenyl)aminium hexauorophosphate, DCM, 30 min, rt; (h)387 thianthrene+ FeCl4, DCM, MeCN, 30 min, rt; (i) thianthrene+
GaCl4, DCM, acetonitrile, 30 min, rt; (j)388 pyridinium tribromide, benzene, EtOH, 3 h, reux; (k) (1) n-BuLi, benzene, diethyl ether, 15 min, rt,
(2) (tBuNO)2, overnight, rt; (l) Ag2O, dry DCM, 2 h, rt; (m) tris(4-bromophenyl)aminium hexachloroantimonate, DCM, 30 min, rt.
CF3SO3D at room temperature, gradual deuteration of 77.3

takes place ortho to oxygen bridges (C19.3), indicating that
this carbocation can react with positively charged electrophiles.395,396 The pertinent dication, C19.4, was generated by
using 100% magic acid (1:1 FSO3H/SbF5) in SO2 at 60 C.
The origin of the stability of trioxatriangulenium cations can be
traced to the extensive delocalization of positive charge, which
was investigated by Wilbrandt et al. using vibrational spectroscopy and theoretical methods.397
Treatment of carbocation 77.3a with MeLi led to compound
C19.5, which was further converted into rigid molecular
cavities, C19.6ab, by Siegel and co-workers.399401 Related
work from Freedman, Luk, et al. focused on the supramolecular
properties of chiral bowls, such as C19.7.402 In 1997, Krebs et
al.398 obtained the tert-butyl-substituted sesquixanthydryl cation
77.3b, which could be easily reduced using sodium borohydride
or methylated with MeLi in the presence of a catalytic amount
of copper(I) iodide. For compound 77.4a, a pyroelectric
coecient of 0.5 0.4 C m1 K2 was determined in the
temperature interval 2435 C. An extensive crystallographic
study of 77.3ab salts with a broad range of anions, reported in
1999 by Krebs and co-workers, revealed planar structures of the
cations and anion-dependent packing patterns.403 Photophysical and electron-transfer properties of 77.3a were
nitroxide-substituted neutral triradical 76.11, which was

obtained from 76.7 in three steps.388 Because of strong
antiferromagnetic exchange coupling, the 76.11 triradical had a
doublet ground state, which was changed to a diradical cation
triplet 76.12, upon one-electron oxidation of the -conjugated
trioxytriphenylamine skeleton using tris(4-bromophenyl)aminium hexachloroantimonate.
Sesquixanthydrol 77.2a, rst reported in 1964 by Martin
and Smith, was originally obtained by heating carbinol 77.1a
with pyridine hydrochloride, followed by treatment with base
(Scheme 77).389 At pH 9.05, a 50% dissociation of 77.2a into
the corresponding cation 77.3 was observed in the borate
buer. By reducing 77.3 with Cr2+, Martin, Gutowsky, et al.390
as well as Feldman and Bowie391 produced the covalent dimer
C19.2, which showed no signicant dissociation into radicals at
room temperature, either in the solid state or in solution. At
high temperatures in diglyme and xylene solutions, reversible
dissociation into radicals was however observed by Muller and
co-workers. 392 77.3 is considerably more stable than
nonbridged triarylmethyl cations. For instance, Carey and
Tremper were not able to reduce it by hydride transfer from
Et3SiH at room temperature,393 although prolonged reuxing in
acetic acid did produce the expected sesquixanthene 77.4a.394
Pagni and co-workers showed that, upon treatment with
BH
Chemical Reviews
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Scheme 77. Synthesis of Sesquixanthydrol Derivativesa
a
Reagents and conditions: (a)389 (1) pyridine hydrochloride, 1 h, 205 C, (2) NaOH, H2O; (b)398 (1) HCl, H2O, 4 h, reux, (2) pyridine
hydrochloride, 2.5 h, 130 C; (c) HPF6 (60% w/w), diethyl ether, 030 min; (d) (1) NaBH4, 1,2-dimethoxyethane, 45 min, (2) diethyl ether, 30
min; (e) NaBH4, 1,2-dimethoxyethane, 1 h, reux; (f) CuI, CH3Li, Ar atm, THF, 1 h, 78 C; (g) LiI, N-methyl-2-pyrrolidone, 4 h, 170 C; (h)
MeLi, THF, 20 h, rt.
investigated by Gopidas and Dileesh.404 The study revealed that

both the singlet and the triplet excited states of 77.3a can
accept an electron from donor molecules, leading to the
formation of the donor radical cation and the radical C19.1. In
aqueous solution, 77.3a was found to photo-oxidize DNA
nucleosides such as guanosine or adenosine. Further investigation into the excited-state properties of trioxatriangulenium
cations, made by Reynisson et al.,405 revealed a JahnTeller
distortion in the S1 state, sizable uorescence quantum yields,
and low-temperature phosphorescence. 77.3a was also shown
to intercalate and photooxidize duplex and quadruplex
DNA.406408
In 1998, Laursen et al. described a series of aminosubstituted carbenium ions 77.6ac, obtained by ring closure
of the cationic precursors 77.5ac in the presence of LiI in Nmethyl-2-pyrrolidone.409 With a pKR+ of 19.7, the 77.6a cation
is very stable, and its electrochemical reduction was found to
lead to rapid dimerization. The X-ray crystal structure of 77.6b
revealed a planar geometry of the cation, which formed innite
tilted stacks, segregated with PF6 anions. Compounds 77.3a,
77.4d, and 77.6a were used to form highly ordered adlayers on
Au(111) surfaces.410
D3h symmetric C19.8ad ions, prepared in 2005 by Laursen,
Harrit, et al., showed photophysical properties resembling those
of rhodamines with respect to band shape, absorption
coecient, uorescence quantum yield, and excited-state
lifetime.411 Distinct blue shifts in their absorption together
with red shifts in the uorescence and reduced emission
quantum yields were observed for these systems with the
decreasing polarity of the solvent. The observed eects were
rationalized in terms of in-solution aggregation eects. The
electronic properties of ion pairs of C19.8d with Cl, BF4,
PF6, and TRISPHAT anions were subsequently investigated
using spectroscopic and theoretical methods.412 The absorption
spectrum of free C19.8d contains one degenerate electronic
transition in the visible region, which upon ion-pair formation
was split into two bands, whose separation depended on the

size of the anion. The splitting of the electronic states in
trioxatriangulenium dyes in nonpolar solvents could be fully
explained by an internal Stark eect in the formed ion pairs.
Laursen, Simonsen, et al. synthesized amphiphilic trioxatriangulenium salts carrying two (C19.9ab) or four (C19.9c)
n-decyl chains and the PF6 anion.413 In LangmuirBlodgett
(LB) lms, they self-assembled into columnar aggregates, with
the cations standing upright with respect to the water surface.
Compounds C19.9a and C19.9b form well-ordered 2D
crystalline monolayers with a repeat distance along the
columnar aggregates of only 3.45 . For both compounds,
a small tilt of 89 for the planar carbenium ions relative to the
columnar axis was deduced. Multilayer LB lms were prepared
from C19.9ab on lipophilic glass by standard vertical
dipping.414 Grazing incidence X-ray diraction (GIXD)
measurements showed that the planar organic cores, despite
their positive charge, form closely packed columns with a
repeating distance of 3.45 reported earlier.413 Specular Xray reectivity (SXR) revealed the LB multilayers to consist of
Y-type bilayers with a thickness of 31 for C19.9a and 41
for C19.9b. GIXD and polarized UVvis absorption and
emission spectroscopy showed that the columnar aggregates in
the LB lms were oriented along the dipping direction. This
alignment was attributed to shear eects during LB transfer.
The main absorption band of the LB lms was blue-shifted as
compared to that in solution, while the uorescence was redshifted by more than 100 nm. These ndings suggested the
presence of H-aggregates, in agreement with the cofacial
packing derived from the X-ray measurements.
Self-assembly of the amphiphilic -conjugated carbenium ion
C19.9a in aqueous solution selectively led to discrete and
highly stable nanotubes or nanoribbons and nanorods,
depending on the nature of the counterion (Cl vs PF6,
respectively).415 The nanotubes formed by the Cl salt in
aqueous solution had an exceptionally well-dened (29 2 nm
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Chemical Reviews
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Chart 19. Derivatives of Heteratriangulenes with Oxygen Atoms390,395,396,399401
Scheme 78. Synthesis of Trihydroxytrioxatriangulenea
in outer diameter), unilamellar tubular morphology. Compound C19.9c was aligned by simple spin-casting on substrates
with friction-transferred PTFE layers.416 These uorescent
crystalline thin lms showed near-perfect macroscopic alignment on centimeter-large areas. C19.9c organizes into a layered
structure with columns of alternating C19.9c cations and PF6
anions. The highly anisotropic distribution of the PF6
counterions dictates the orientation and coupling of the optical
transitions. By use of a uorescent dopant, very ecient energy
migration was demonstrated to take place in the thin lm.
In 2010, the synthesis of trioxatriangulenium salts C19.10a
d with one or two dialkylamino donor groups attached to the
resonant peripheral positions was reported by Srensen and
Laursen (Chart 19).417 The dyes with two amino groups
(C19.10cd) were found to be strong uorophores with blueshifted emissions relative to rhodamine B. The monosubstituted compounds C19.10ab were only weakly uorescent.
In 2012, Laursen, Simonsen, et al. reported the formation of
uniform and highly stable unilamellar vesicles (ULVs)
consisting of 1,2-dimyristoyl-sn-glycero-3-phosphocholine
(DMPC) and 5 mol % of C19.9d.418
By extending the original Martin synthesis to the tris(2,4,6trimethoxyphenyl)methylium salt 78.1, Laursen et al. produced
the trihydroxytrioxatriangulenium analogue, which was isolated
in its neutral keto form 78.2 (Scheme 78).419 Compound 78.2
is slightly soluble in common organic solvents and can be
converted into the water-soluble dianion 78.3 by treatment
with base. 78.3 possesses a planar D3h symmetry. All
protonation states of 78.3 are uorescent. The species may
be viewed as an extended uorescein analogue with a blueshifted absorption, characterized by comparable extinction
coecient and uorescence quantum yield.
Aromatic nucleophilic substitution of methylenium cations
79.1 and 79.6 was shown by Laursen and Krebs to provide
triazatriangulenium cations of the general structure 79.5
(Scheme 79).420 Partially bridged intermediates 79.24 could
be isolated in the presence of a smaller amount of the amine.
(The chemistry of diheterahelicene intermediates such as 79.4
is discussed in section 5.2.) Highly stable triazatriangulenium
carbocations, synthesized by Nicolas and Lacour, were
characterized by pKR+ values higher than 20 (79.5cf) and
could be employed as phase transfer catalysts.421 Maeda et al.
Reagents and conditions:419 (a) pyridinium hydrochloride, 2.5 h, 170

C; (b) 1 M KOHaq, tetrabutylammonium bromide, 12 h, rt.
reported solid-state charge-by-charge assemblies consisting of

planar 79.5b and 79.5gh cations combined with supramolecular anions containing BF2 complexes of 1,3-dipyrrolyl1,3-propanediones.422,423
Laursen et al. used compound 79.5g to form highly ordered
thin lms by direct spin-casting onto rotating substrates.424
These homogeneous and crystalline thin lms showed
macroscopic order over centimeters. The crystal structures of
the 79.5BF4 salts were investigated for the propyl, 3methylpentyl, and octyl derivatives. In all cases, the molecules
were unusually packed into hexagonally ordered bilayers, with
the rigid discotic 79.5 cores organized coplanarly in sheets
separated by perpendicularly oriented alkyl chains. The
structure of the thin lms was investigated by optical
spectroscopy, X-ray reectometry, and grazing incidence Xray diraction. It was conrmed that the 1530 nm thick lms
maintained the lamellar structure of the bulk crystals, showed
good atness on macroscopic length scales, and were
completely ordered relative to the substrate. The triazatrianguBJ
Chemical Reviews
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Scheme 79. Triazatriangulenes and Their Mixed-Heteroatom Analoguesa
Reagents and conditions: (a)420 methylamine, N-methylpyrrolidone, 20 h, rt; (b) n-propylamine, N-methylpyrrolidone, 45 min, reux; (c) benzoic
acid, methylamine, N-methylpyrrolidone, Ar atm, 924 h, reux; (d)425 NaH, aniline, 20 min, 200 C; (e) (1) 79.7c, naphthalene-1-boronic acid,
toluene, 80 C, (2) K2CO3, (PPh3)2PdCl2, H2O, 12 h, reux; (f)426 (1) molten pyridine hydrochloride, pyridine, 1 + 4 h, 200 C, (2) KOH, water;
(g)427 H2SO4.
Chart 20. Mixed-Heteroatom Triangulenium Derivatives428,436
In 2001, Laursen and Krebs synthesized a series of mixedheteroatom triangulenium 79.9, 79.10, and 79.12 (Scheme
79).426 These compounds were prepared from appropriate azabridged precursors using the pyridine hydrochloride method.
pKR+ values of 14.5 and 19.4 were determined for compounds
79.9 and 79.10, respectively. In the synthesis of 79.12,
spontaneous debenzylation occurred, leading to a neutral
product. A structurally related species, 79.15, was obtained in
1980 by Reznichenko, Shapkin, and Popov via stepwise
cyclization of the 1,8-disubstituted anthraquinone 79.13.427
Dileesh and Gopidas studied uorescence quenching and
laser ash photolysis of stable azatriangulenium ions 79.10 and
C20.12 (Chart 20).428 Their results indicated that 79.10 acts
as an excited-state electron acceptor, whereas C20.2 is an
excited-state electron donor. C20.1 could act as an acceptor or
lenium molecules are electroactive, and showed intense

uorescence and ecient exciton transport in the lms.
N,N,N-Triaryl-substituted triazatriangulenium dyes were
reported in 2012 by the Laursen group (79.78).425 The
synthesis of 79.7 was achieved by heating the tris(2,6dimethoxyphenyl)methylium ion in various anilines in the
presence of NaH. Aryl derivative 79.7c was further functionalized using SuzukiMiyaura coupling, leading to 79.8. Singlecrystal structures, obtained for 79.7a and 79.7c, showed
torsional angles larger than 80 between the cation core and the
aryl substituents. The 79.7 dyes emitted in the red region of the
spectrum (fl = 560 nm) and showed a surprising 3-fold
increase in uorescence quantum yields (>50%) when
compared to the alkyl-substituted salts.
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Chemical Reviews
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donor in photoinduced electron transfer (PET) reactions. The

research revealed that the replacement of oxygen atoms by Nalkyl moieties leads to a gradual shift of the photoinduced
electron transfer behavior from an acceptor to that of a donor.
The photophysics of azaoxatriangulenium uorophores were
further characterized by Laursen et al.429 Their work showed
that the optical properties of these triangulenium dyes were
solvent-independent in both absorption and emission but were
aected by the symmetry of the chromophore. The C2v
symmetric dyes, azadioxatriangulenium 79.10 and diazaoxatriangulenium C20.1, have high emission anisotropies,
uorescence lifetimes around 20 ns, and uorescence quantum
yields of 50%. The trioxatriangulenium (77.3a) and
triazatriangulenium (C20.2) dyes, nominally of D3h symmetry,
have uorescence lifetimes around 10 ns and uorescence
quantum yields of 1015%. A amino-substituted azadioxatriangulenium ion C20.4 was shown to have very high stability,
with a reported pKR+ value close to 25.430 This ion showed an
intense absorption at 458 nm and a high uorescence quantum
yield. The chloride analogue of 79.10, C20.6a, exhibited an
enhancement of uorescence emisson induced by selfassembled silver nanoparticles on a gold lm.431,432 In another
application, the use of the substituted azadioxatriangulenium
C20.6b in combination with time-correlated single-photon
counting detection was used to eliminate autouorescence
background from uorescence tissue images.433435
By methylation of an unsymmetrically N-substituted
diazaoxatriangulenium cation, Lacour et al. produced a chiral
cup-shaped diazaoxatricornan derivative C20.3, which was
isolated in the racemic form.436 The enantiomers of C20.3 were
chromatographically separated on a chiral stationary phase, and
the absolute conguration of ()-(S)-C20.3 was determined by
comparison of the experimental and theoretical vibrational
circular dichroism (VCD) spectra. The isolation of ()-(S)C20.3 and (+)-(R)-C20.3 constituted the rst report of a
nonracemic closed-capped chiral bowl molecule for which the
chirality was due to the intrinsic dissymmetry of the central
core of the structure only.
Further work by Krebs on functionalized azadioxatriangulenium systems such as C20.5a437 enabled the synthesis of large
amphiphiles C20.5c (MW 3000).438 These molecules
consisted of a polar cationic chromophore (A-domain), which
serves to organize the assembly at the surface, and a
hydrophobic part, designed as a light-harvesting antenna (Jdomain). By compression of the molecules at the waterair
interface in a Langmuir trough, regular pressurearea isotherms
were obtained. The monolayers were transferred in the
condensed state to a conductive substrate yielding closely
packed LangmuirBlodgett (LB) lms with a thickness that
could be varied between 4 and 8 nm depending on the
molecular size. It was found that the lifetime and quantum yield
for the light harvesting and energy transfer increased
signicantly in the JA-assembly as compared to mixtures of
separate A- and J-domains. The emission from the A-domain
was increased 20 times when covalently connected to the lightharvesting J-domain and a further 23 times when going from
solution to the solid LB-lm.
Magnussen, Herges, et al. proposed a versatile concept for
the preparation of well-dened functional adsorbate layers on
metal surfaces using triazatriangulene units as pedestals to
provide perpendicular orientation of the attached functions
relative to the surface (Figure 3).439442 To prove this concept,
diversely substituted triazatriangulenes of the general structure
Figure 3. The platform approach to the construction of functional

monolayers. Adapted from ref 439. Copyright 2009 American
Chemical Society.
C21.2 were synthesized by nucleophilic attack at the central C

atom of triazatriangulenium ions C21.1ad (Chart 21). As
Chart 21. Triazatriangulenes for Application in
Photoswitchable Self-Assembled Monolayers439442
shown for molecules with side chains of dierent lengths or

substituents, this approach allowed the preparation of very
stable, hexagonally ordered adlayers on Au(111). The
intermolecular spacings in these adlayers were independent of
the attached functions with the latter being oriented
perpendicular to the Au surface.
Several sulfur-bridged heterocyclic carbocations of the
acridinium and triangulenium family were prepared by Lacour
et al., who used 80.4 tetrauoroborate as the key synthetic
intermediate443 (Scheme 80, for an earlier report of a related
structure, 80.9, see ref 444). Using simple aromatic nucleophilic
substitution reactions, salts 80.57 were obtained in moderate
to good yields. From the X-ray structural analysis of 80.3, bond
lengths between sulfur and carbon atoms were conrmed to be
much longer than those of CO or CN bonds in analogous
frameworks. These larger bond lengths caused a distortion of
the sulfur-containing six-membered ring, which was invoked to
explain the relative lack of stabilization of the resulting
carbenium ions. A comparison between electronic absorption
spectra of the sulfur-bridged dyes and their aza analogues
showed a ca. 50 nm shift toward the low-energy region upon
introduction of the sulfur bridge.
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Scheme 80. Sulfur-Bridged Triangulenesa
a
Reagents and conditions: (a)443 (1) lithium cyclohexyl(isopropyl)amide, THF, 10 min, 20 C, (2) 1-bromo-2-methoxybenzene, 20 h, 25 C; (b)
(1) 1,3-dimethoxybenzene, n-BuLi, TMEDA, toluene, 1.5 h, 0 C, (2) 24 h, rt; (c) HBF4, EtOH, 60 min, rt; (d) aniline, benzoic acid, 20 h, 110 C;
(e) aniline (neat), 22 h, 190 C; (f) pyridine hydrochloride, 4 h, 200 C; (g) MeLi, THF, 4 h, 025 C.
Scheme 81. Synthesis of Phosphatriangulenesa
Reagents and conditions: (a)445 95% t-BuOK, N-methyl-2-pyrrolidone, 1 h, 200 C; (b) 35% H2O2, chloroform, overnight, rt; (c)448 30% H2O2,
chloroform, 15 h, rt; (d) CH3I, Cs2CO3, DMF, 15 h, rt; (e) Fe powder, Br2, DCM, 22 h, rt; (f) BBr3, DCM, 15 h, rt; (g) t-BuOK, DMF, 23 h, 140
C; (h) CuI, Pd(PPh3)4, phenylacetylene, THF, Et3N, 62 h, 60 C.
a
column. Compound 81.9 possesses a chiral concave structure

and exhibits chiroptical properties with a large anisotropy. In
the cocrystal with C60, four molecules of the enantiopure 81.9
perfectly wrapped the surface of C60. The analysis of the
induced CD signal of a guest fullerene derivative indicated the
transfer of the chiroptical properties of 81.9 to the guest.
A boron-containing triangulene 82.5, which can be viewed as
a planarized triarylborane derivative, was synthesized in 2012 by
Wakamiya, Yamaguchi, et al. (Scheme 82).449 Their synthesis
started from the dihydroborinine derivative 82.1, and involved
FriedelCrafts cyclization as the key bond-forming step. An
extension of the above strategy led to the diboracoronene
derivative, 9,10-diphenyl-9,10-dihydro-9,10-diboraanthracene
82.8. These compounds were stable toward air, water, and
amines, despite the absence of steric protection of the B atoms,
and showed characteristic structural, electronic, and photophysical properties. In addition, upon treatment with the
uoride ion, these compounds underwent a plane-to-bowl
conversion in a controlled manner. In subsequent work, a
radical anion of 82.5 was generated by reduction with
potassium, and characterized structurally and spectroscopically.450 It was found that the delocalization of spin density in
Phosphatriangulene 81.2 was obtained in 1997 by Krebs and

co-workers, by heating triarylphosphine 81.1 with tBuOK.398,445 81.2 was oxidized to the respective P-oxide,
81.3, using hydrogen peroxide in chloroform. 81.2 showed
permanent polarization in the solid state, and its pyroelectric
coecient was found to be 3 2 C m2 K1. A molecular
dipole moment of 4.7 D was determined for compound 81.2 in
the solid state, corresponding to a 42% dipole moment
enhancement as compared to the dipole moment measured in a
chloroform solution.446 Atomic-resolution images of 81.2
adsorbed on Ag(111) revealed three distinct binding
congurations, corresponding to dierent orientations of the
nonplanar triangulene structure relative to the substrate
surface.447 An acetylene-substituted derivative 81.8 was
reported in 2014 by Yamamura, Saito, and Nabeshima.448 In
their approach, 81.1 was initially converted into the respective
P-oxide and methylated, to permit regioselective bromination of
the aryl rings. The tribromo derivative 81.6 was then
deprotected and cyclized, to yield the prefunctionalized
triangulene 81.8. In the nal Sonogashira coupling step,
compound 81.9 was obtained in 21% yield as a racemic
mixture, and separated into enantiomers on a chiral HPLC
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Chemical Reviews
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Scheme 82. Synthesis of Boron-Doped Pyrenoids and Related Systemsa
Reagents and conditions: (a)449 (1) 2-bromo-1,3-di(propen-2-yl)benzene, n-BuLi, toluene, 0 C, (2) 6 h, rt, (3) 82.1 or 82.6, 20 h, rt; (b)
Sc(OTf)3, 1,2-dichloroethane, 24 h, reux; (c) CrO3, AcOH, 1 h, reux; (d) (1) TiCl4, Me2Zn, DCM, 30 min, 25 C, (2) 82.4, 12 h, 25 C;
(e)451 (1) nBuLi, ether, 40 min, 78 C, (2) 82.10, ether, rt; (f) 1,1-azobis(cyclohexanecarbonitrile), tris(trimethylsilyl)silane, toluene, 15 h, 110
C; (g) (1) FeCl3, CH3NO2, DCM, 0 C; (h) (1) n-BuLi, ether, 45 min, 78 C, (2) BF3Et2O, (3) rt; (i) n-Bu3SnH, 1,1azobis(cyclohexanecarbonitrile), toluene, 15 h, 120 C.
a
Scheme 83. Synthesis of Flavanthrone and Its Derivativesa
Reagents and conditions: (a)454 Cu, naphthalene, 45 min, 220240 C; (b) H2SO4, 50 C; (c)456 30% NH3, CuSO4, 40 h, 230240 C; (d)457
molten KOH, 20 min, 295305 C (65%); (e)458 SbCl5, nitrobenzene, 1 h, reux; (f)459 (1) H2SO4 (conc.), (2) H2O, (3) 2% lye, Na2S2O4, without
air, 1 h, 75 C, (4) caustic soda, air, 70 C; (g)460 zinc dust, ZnCl2, NaCl, 10 min, 280290 C; (h) (1) zinc dust, pyridine, o-dichlorobenzene, 10
min, reux, (2) benzoyl chloride, 30 min, reux; (i) (1) 4% NaOH, 2% Na2S2O4, 20 min, 2075 C, (2) benzoyl chloride, 2 h, 2075 C; (j) (1)
triisopropylsilylacetylene, dry THF, n-BuLi, 1 h, 0 C, (2) 83.3a, overnight, rt, (3) NaI, NaH2PO2H2O, AcOH, 4 h, reux.
a
with the electron-accepting boron center, yielding broad

absorption bands over the entire visible region and a
uorescence in the visible/near-IR region. In addition, 82.11
showed a dramatic change of its properties upon formation of a
tetracoordinated borate, leading, for instance, to a thermochromic behavior in the presence of pyridine. Compound 82.9 was
also used for the preparation of a symmetrical precursor 82.14,
which yielded a very unusual nonbenzenoid framework 82.15
this radical was more extensive than in its nonfused analogues,

and that it adopted a bowl-shaped, rather than planar,
conformation.
A related pyrenoid molecule 82.13, in which the
tricoordinated boron atom was embedded in a fully fused
polycyclic -conjugated skeleton, was prepared from the triaryl
precursor 82.11 in a sequence of reductive and oxidative CC
couplings.451 This compound, which is as stable as 82.5 and
82.8, combines an electron-donating -conjugated skeleton
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Chemical Reviews
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Chart 22. Selected Azapyrenoid Pigmentsa
when subjected to a radical-promoted intramolecular homocoupling.

4.2. Azapyrenoids
Flavanthrone 83.3a, a common yellow vat dye, known under a

variety of commercial names, was rst obtained by Bohn in
1901.452 The original procedure, which involved fusion of 2aminoanthraquinone with alkali, produced avanthrone at
temperatures of 300350 C, whereas the blue indanthrone
was formed at 220250 C.1 Early industrial syntheses, which
used strong Lewis acids, such as SbCl5 or TiCl4, for promoting
the condensation, were replaced with a procedure involving 1chloro-2-aminoanthraquinone and phthalic anhydride. The
extended fused-ring structure of 83.3a was rst established by
Scholl in 19073 and conrmed by a later X-ray crystallographic
analysis.453 In their ultimate synthetic proof, Scholl and
Dischendorfer prepared avanthrone in two steps, by rst
converting 1-chloro-2-benzylidenaminoanthraquinone into the
dianthraquinonyl derivative 83.2a, and dehydration of the latter
intermediate to 83.3a.454 A systematic analysis of the
dehydration reaction was carried out by Kratochv l, Slav k,
and Nepras.455 A range of substituted avanthrones was
subsequently prepared including the dibromo,456 di-tertbutyl,457 and dimethyl458 derivatives 83.3bd. A dierent
route to avanthrones involves intramolecular FriedelCrafts
acylation of diazapyrene intermediates such as 83.5.459
Zinc reductions of avanthrone, reported in 1968 by Aoki,
furnished two leuco-type derivatives 83.4ab.460 A TIPSethynyl leuco-derivative, 83.4c, was reported in 2013 by
Briseno and co-workers.461 The latter compound was prepared
by lithium acetylide addition to 83.3a followed by reductive
aromatization with NaI/NaH2PO4. Along with related undoped
PAH derivatives, compound 83.4c was tested as a semiconductor material in single-crystal FET devices, yielding the
hole mobility of up to 0.14 cm2 V1 s1.
Dinylin 84.2, a smaller fused system related to leucoavanthrone derivatives, was reported in 1940 by Rieche,
Rudolph, and Seifert (Scheme 84).462 Their synthesis involved
Azapyrene substructures are indicated in red.
lesser-known dyestus, see ref 464). One of the directions

taken in the dyestu research focused on increasing the number
of heteroatom sites, leading to systems such as C22.4465 or
C22.5.466
In the 1970s, Buu-Ho et al.467 and Jacquignon and coworkers468,469 synthesized a series of benzo- and naphtho-fused
2-azapyrenoids 85.2, 85.4, and 85.6 (Scheme 85). All
compounds were obtained using a common strategy, by baseinduced thermal cyclization of appropriate 9-(2-chlorophenyl)acridine precursors. An isomer of 85.2a, with a dierent benzofusion pattern, was reported by Arbuzov and Grechkin.470
Cationic pyrenoids with the nitrogen embedded inside the
fused core were reported in 1979 by Katritzky and co-workers
(Scheme 86).471 A range of derivatives, including the monoaza
and diaza systems 86.2a and 86.4, were prepared by oxidative
photocyclization of the corresponding 1,2,6-triarylpyridinium
cations.472 The planarity of the fused core in these systems was
established on the basis of an X-ray structural analysis
performed for 86.4a.471 By using the same synthetic strategy,
other systems were subsequently obtained, such as 86.5472 or
the dithieno derivative 86.6.473 The cationic benzo[1,2]quinolizino[3,4,5,6-def ]phenanthridin-15-ium motif, present in
86.2, was reported in 2007 by Zhi, Mullen, et al. to provide a
controllable self-assembly into nanobers and nanotubes.474 By
drop-casting methanolic solutions of the chloride salts 86.2b
and 86.2d onto a silicon wafer, it was possible to generate bers
with a cylindrical and ribbon-like shape, respectively. WAXS
data revealed a dierent mode of packing in the two ber types,
with the ribbon bers of 86.2d adopting a lamellar structure.
The morphology of the ribbons could be further modied by
changing the counteranion, and the tetrauoroborate salt 86.2e
yielded nanotube-like aggregates constructed by lamellar
packing. In contrast, the eect of counteranion on ber packing
in 86.2c was insignicant. In subsequent work, the Mullen
group explored the self-organization of cations in the series
86.2fj as a function of the counteranion.475 Columnar
mesophases were observed for 86.2ij, with a staggered
arrangement of consecutive cation molecules in the stacks,
analogous to that observed in the crystal for 86.2f.
Interestingly, the regioselectivity of photocyclization in
hexaaryl-substituted pyridinium cation 86.7 is altered, and
results in fusion of meta and para substituents, as shown in
2010 by Laine, Campagna, et al.476 The resulting -expanded
Scheme 84. Synthesis of Dinylina
Reagents and conditions: (a)462 H2SO4 (conc.), H2O, 5 h, 130 C;

(b) aniline, 2 h, reux.
heating bisacetamino derivative 84.1 with concentrated sulfuric

acid. Reuxing 84.2 with aniline was proposed to result in the
formation of the substituted product 84.3. Pyranthridone
C22.1, synthesized by Scholl and Dischendorfer in 1918, as the
intermediate member of the pyranthroneavanthrone series,
is an early example of an extensively fused 4-azapyrene
derivative (Chart 22).463 The anthra[2,1,9-mna]acridin-14-one
motif, which contains the 1-azapyrene substructure, is found in
a range of industrial vat dyes, exemplied by two indanthrene
pigments, Olive Green B C22.2 and Olive T C22.3. The
former of these dyes is synthesized by condensing 3bromobenzanthrone with 1-aminoanthraquinone1 (for a
discussion of base-induced oxidations of this type and some
BO
Chemical Reviews
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Scheme 85. 2-Azapyrenoidsa
Reagents and conditions: (a)467469 NaOH, benzo[h]quinoline, 4 h, 350360 C.
Scheme 86. Photobiscyclization of 1,2,6-Triarylpyridinium Cationsa
Reagents and conditions: (a)472 h (300 W), MeOH, 24 h, rt; (b)472 h (300350 W), MeOH, 1524 h, rt; (c)476 UV irradiation, MeOH/DCM,
O2 gas; (d)477 (1) reactant as BF4 salt, MeOTf, MeCN, rt, (2) KPF6, H2O.
cation 86.8 had a saddle-like distortion caused by orthosubstituents, but nevertheless showed -stacking dimerization
in the solid state. The fusion caused a moderate red shift of
uorescence (maxem = 455 and 479 nm in 86.7 and 86.8,
respectively), accompanied by a reduction of quantum yield
(from 0.48 to 0.13). This result was in opposition to the eect
of fusion in 86.2f, which showed a blue-shifted and
considerably stronger luminescence in comparison with 86.1f.
Subsequent work from the Laine group showed that, in contrast
to N-pyridine-substituted pyridinium cations 86.3, the Nmethylated derivative 86.9 was photostable and did not
undergo oxidative cyclization to 86.10.477 The latter species
could however be obtained by direct methylation of 86.4a. This
dicationic product was characterized by two reversible oneelectron reductions, and a red-shifted electronic spectrum with
a charge-transfer character.
In 1940, Waldmann and Hindenburg described the synthesis
of two N,N-dihydro-3,10-diazapyrene derivatives C23.12
(Chart 23).478 Both compounds were prepared via a
condensation reaction between 7,10-dichlorotetracene-5,12dione and benzotriazole or naphthotriazole, respectively,
followed by a double GraebeUllmann cyclization step.
C23.4 was described in 1971 by Tsuchiya et al. as one of the
products obtainable in the photocyclization of tetraphenylpyr-
Chart 23. Diazapyrene Derivatives
idazine 57.3 (Scheme 57, section 3.3).299 The yield of C23.4

was maximized (up to 60%) by performing the irradiation in
methanol. The structure of 1,6-diazapyrene derivative C23.3
was determined crystallographically by Ammon and Reid.479
This compound was obtained in low yield from a fairly unusual
BP
Chemical Reviews
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Scheme 87. Synthethic Routes to Azapyrenesa
a
Reagents and conditions: (a)164 copper bronze, diethyl phthalate, dioxane, 57 min, reux; (b)481 benzylamine, pyridine, 1.5 h, reux; (c)480 85%
N2H4 hydrate, pyridine, 1 h, reux; (d) Al, cyclohexanol, overnight, reux; (e)482 (1) KOH, MeOH, 16 h, reux, (2) K2CO3, 0.5 h, rt, (3) HCl, (4)
P4O10, trichlorobenzene, 4 h, reux; (f) benzaldehyde, 10% KOH in MeOH, pyridine, 1 h 15 min, reux; (g) Pd/C; (h)483 250 C; (i) 5% Pd/C,
xylene; (j)485 CuI, dioxane, microwave irradiation (300 W), 1 h, 150 C; (k) Pd(OAc)2, PPh3, K3PO4, DMF, 4 h, 130 C; (l)484 NH4OAc, AcOH, 15
min, reux; (m) N2H4H2O, 2-propanol, AcOH, 24 h, reux.
Scheme 88. Synthesis of 1,8-Diazapyrenesa
Reagents and conditions: (a)486 PPA, 324 h, 175180 C; (b) aniline, reux.
dimerization reaction of 2-(4-methylphenyl)quinoline induced

with phenyllithium. Nonbonded interactions in the fjord
regions of C23.3 are apparently responsible for the substantial
out-of-plane distortions of the ring system, observed in the

solid state.
BQ
Chemical Reviews
Review
Scheme 89. Diheterapyrenoids from Anthraquinonesa
The thiazepine method, described in 1958 by Galt, Loudon,

and Sloan, provided, in addition to the perylenoid derivative
36.2 (section 3.1), also the isomeric diazapyrenoid 87.2
(Scheme 87).164 The requisite bisthiazepine 87.1 was obtained
from 1-chloro-4-nitroanthraquinone in a reaction with sodium
o-aminophenyl sulde, and subsequently heated with copper
bronze to yield the product. Starting from pentaphene5,8,13,14-tetraone 87.4, Tilak, Unni, and Venkataraman
synthesized the pyridazine fused system 87.6 as a potential
carcinogenic agent.480 87.4 was reuxed with hydrazine
hydrate, and the resulting quinone 87.5 was subjected to
reduction with aluminum tricyclohexoxide, which produced the
desired, lemon-yellow 87.6. A monoaza analogue, 87.3, was
synthesized by the Scholl group in 1936, by heating 1,2phthaloylanthraquinone 87.4 with benzylamine in boiling
pyridine (Scheme 87).481
Diketodiazapyrene derivatives 87.910, reported in 1962 by
VanAllan, Reynolds, and Adel,482 were obtained by double
electrophilic cyclization of the phenazine derivative 87.7,
followed by a reaction with benzaldehyde, and the optional
catalytic debenzylation. A structurally similar system, 87.13, was
synthesized by Kappe, Linnau, and Stadlbauer via condensation
of 1,2,3,4-tetrahydrophenazine 87.11 with a substituted
malonate, followed by dehydrogenation.483 Interestingly, an
analogous condensation performed on phenazine itself yielded
a diazaperylene derivative 33.14176 (section 3.1), isomeric to
87.13. Di- and triaza- systems 87.18ab were obtained by
Deady and Smith by condensing the respective tetracyclic
precursors 87.17ab with ammonium acetate.484 Analogous
condensations with hydrazine were found to yield the
corresponding diazepines 87.19ab.
Highly fused perimidines, such as 87.16, were prepared by
Fujii, Ohno, and co-workers in 2011.485 The reported two-step
procedure consisted of a copper-catalyzed double annulation of
87.14 with 1,8-diaminonaphthalene, combining aldehyde
condensation with hydroamination of the ortho-ethynyl
substituent, followed by a palladium-catalyzed CH arylation/dehydrogenation.
Acid-catalyzed cyclizations of anthraquinone and anthrapyridone derivatives, reported by Kazankov, Bernadskii, and
Mustana, yielded benzannulated 1,8-diazapyrenes shown in
Scheme 88.486 Specically, compound 88.8 was prepared in
two steps, by reuxing 88.6 in polyphosphoric acid and
subsequent heating of the intermediate 88.7 in the presence of
aniline. The overall yield of the latter sequence was improved to
64% when the order of steps was reversed. Compounds 88.3
and 88.5ad exhibited intense uorescence, in contrast to 88.8,
which was an appreciable uorescence quencher.
In 1997, Tokita and co-workers used AlCl3-induced
cyclizations of substituted anthraquinones to synthesize two
diheterapyrenes 89.2 and 89.4 (Scheme 89) and a diazaperylenoid (32.8, section 3.1).148 89.2 and 89.4 exhibited
absorption spectra similar to those of their dioxa and dithia
analogues. The original low yields of these reactions were
improved in subsequent work by Shiroishi, Kaneko, et al.487 It
was also found that the endoperoxide 89.5 could be obtained
by UV irradiation of 89.4 in the presence of air. Upon addition
of triuoroacetic acid, compound 89.4 underwent stepwise
protonation to the mono- and dicationic forms. Gradual
elimination of dioxygen from 89.5 was observed upon
protonation.
89.2 is an example of a mixed-heteroatom heterapyrene.
Other fused frameworks of this type include 90.2, reported in
Reagents and conditions: (a)148 hydroquinone, AlCl3, NaCl, 3 h, 150

C; (b)487 hydroquinone, NaCl, AlCl3, 2 h, 180 C; (c) h (300 W
tungsten lamp), air, toluene, 40 min; (d) TFA, 5 h 20 min.
1958 by Barrett and Buu-Ho,488 and the sulfur-containing

anthrone derivatives 90.5ad obtained by Carlini et al. in 1982
(Scheme 90).489 The latter species were derived from
Scheme 90. Synthetic Routes to Diheterapyrenoidsa
a
Reagents and conditions: (a)488 zinc dust, distilled; (b)489 Na2CO3,
DMF, 2 h, reux; (c) (1) DMF, 30 min, 80 C, (2) 36% HCl, NaNO2,
H2O, 2 h, 05 C, (3) CuSO4, 25 C, (4) 3 h, 110 C.
benzanthrones and 1-azabenzanthrones 90.3, which were

functionalized via nucleophilic substitution with o-aminothiophenols, converted to diazonium salts, and cyclized using
Pschorr reaction conditions. Bathochromic shifts were observed
in the absorption spectra of 90.5ad upon the introduction of
nitrogen atoms and methoxy substituent.
1,4,5,8-Naphthalenetetracarboxylic dianhydride 91.1 is a
potentially versatile precursor to heteroatom-containing pyrene
derivatives (Scheme 91). Two isomeric condensation products
of 91.1 with o-phenylenediamine, perinones 91.2ab,
BR
Chemical Reviews
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pyrazole cyclization strategy by Peters and Saidi provided fused

xanthene and thioxanthene systems 91.78.492
A benzo-fused 1,3b,4-triazapyrene 92.2, reported in 1964 by
Partridge, Slorach, and Vipond, was obtained by heating the
perimidine derivative 92.1a with sodium aluminum chloride
(Scheme 92).493 In 1996, Dutt and Rao used a similar strategy
for obtaining the hexacyclic analogue 92.4.494 The latter species
was synthesized from 92.1a, which was cyclized with
triuoroacetyl ketene diethylacetal to yield 92.3. The nal
benzannulation could be achieved by heating 92.3 in diphenyl
ether. Alternatively, both cyclizations could be performed in a
single step, providing an improved overall yield.
Several triazapyrenoids were prepared by Kazankov and
Bernadskii in their work on pyridonoanthrapyrimidines
(Scheme 93).156 93.1 was cyclized with aniline to form 93.2,
which was in turn acetylated to yield the oxazole 93.4. The
interaction of 93.4 with dimethylamine led to the amidine 93.5,
which was reverted to the oxazole upon heating. Further
examples of pyrenoid frameworks containing multiple nitrogen
atoms include 93.8, obtained by the same authors using a twostep pyrimidine cyclization, a heptacyclic structure 93.9
reported by Ursenau and Teszler,495 and a tetraaza system
93.9 of Dutt and Rao.496
Diagonal -expansion of naphthalenediimides (NDIs)50 is
a versatile concept for elaboration of extended pyrenoid
frameworks. In 2011, Luscombe et al. used a Stille-coupling
polycondensation to create a functionalized NDIphenylene
polymer 94.1.497 Upon acid-catalyzed deprotection, 94.1 was
converted into the nitrogen-rich, ladder-type polymer 94.2.
This material was used for the fabrication of n-channel OFETs,
providing electron mobilities up to 0.0026 cm2 V1 s1,
corresponding to an improvement of 3 orders of magnitude in
comparison with 94.1. The group of Marder used diacyl-NDIs
94.4ab, synthesized via Stille acylation of the 94.3, to prepare
the bis-pyridazino-fused NDI analogues 94.5ab.498 Fusion of
pyridine rings, achieved by means of a double TFSIH-induced
cyclization, was reported in 2013 by Zhang, Zhang, et al.499 (for
related cyclizations, see compounds 36.14 and 37.9 in section
3.1). Starting with diethynyl NDIs 94.6ag, the authors
initially obtained the bis-pyrylium salts 94.7ag, which were
directly converted into the fused products 94.8ag. Derivatives
94.8bf, containing no ferrocenyl appendages, were uorescent
in solution and in the solid state, with solution maxem ranging
from 476 nm (94.8f, F > 0.99) to 637 nm (94.8b, F > 0.06).
Thin lms of 94.8c showed a p-type semiconductor behavior
with hole mobilities reaching 0.0063 cm2 V1 s1. Polymers
based on the 94.8 core were subsequently explored as OTFT
materials by the same group.500
Scheme 91. 2,7-Diazapyrenoids Derived from 1,4,5,8Naphthalenetetracarboxylic Dianhydridea
Reagents and conditions: (a)491 o-phenylenediamine, glacial

CH3COOH, overnight, reux; (b) CH3COONa (anhydrous), butan2-ol, overnight, reux; (c)492 DMF, KOAc, reux.
separable by fractional precipitation, are valuable industrial

pigments.350 They show a marked color dierence, which is
partly due to excitonic interactions between stacked molecules
in the crystal.490 The use of 91.2ab as high-performance
polymerization photoinitiators was explored by Gigmes,
Lalevee, and co-workers.491 In the latter work, a related pair
of isomers 91.4ab was reported, obtainable by the cyclization
of a bis(acetylacetone hydrazone), 91.3. An earlier use of the
Scheme 92. Synthetic Routes to Triazapyrenoidsa
Reagents and conditions: (a)493 sodium aluminum chloride, 1 h, 320 C; (b)494 1,1,1-triuoroacetyl ketene diethylacetal, toluene, 6 h, reux; (c)
diphenyl ether, 3 h, reux; (d) 1,1,1-triuoroacetyl ketene diethylacetal, diphenyl ether, 6 h, reux.
a
BS
Chemical Reviews
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Scheme 93. Synthesis of Triazapyrenesa
Reagents and conditions: (a)156 aniline, 100 C, 2 h; (b) acetic anhydride, AcOH, H2SO4, 20 min, reux; (c) acetic anhydride, AcOH, H2SO4, 1 h,
reux; (d) 50% aq dioxane, 30% HCl, 20 min, reux; (e) NHMe2, dioxane, 1.5 h, 20 C; (f) heating in a capillary; (g) POCl3, DMF, 50 C, 2 h; (h)
NH4OAc, MeOH, 20 C, 30 min.
Scheme 94. NDI-Derived Pyrenoidsa
see Scheme 45, section 3.1). In the initial work of Dewar and
co-workers on BN-embedded PAHs, published in 19591960,
two nonfused BN-embedded pyrenes were obtained, 95.8501
and 95.9.502 The interest in BN aromatics has been revived
recently; however, the majority of available BN pyrenoids still
lack extended ring fusion. In 2007, 3a1-aza-5a1-borapyrenes
95.4ae were obtained by Piers and co-workers, by condensing
boracyclohexadienes 95.2 with bis(ortho-alkynyl)-substituted
pyridines 95.1.503 The products were obtained in two steps,
with or without isolation of the intermediate 95.3, the nal
cyclization of the acetylene substituent being catalyzed with
PtCl2. 95.4ae had an orange-brown color and featured higher
electron anities and smaller band gaps than pyrene. The
individual aromaticity of the pyridine and borabenzene
fragments, assessed using NICS(1) values, was greater than in
the anking C4BN rings. The presence of internal BN units
imparts a dipolar character to these molecules, leading to a
head-to-tail -stacking pattern in the solid state. In subsequent
work, dimeric analogues of 95.4b were synthesized by the Piers
group.504
A tandem intramolecular electrophilic arene borylation
reaction was developed by Hatakeyama for the synthesis of
BN-fused PAH analogues, such as 95.6 and 95.7.505 To obtain
95.6, the authors prepared the diamine 95.5, which was Nborylated with BCl3 and subjected to an intramolecular
electrophilic aromatic borylation. The latter step required
extensive optimization, which revealed that the right combination of Lewis acid and Brnsted base was necessary for eective
cyclization. Both 95.6 and 95.7 adopt a twisted conformation,
which results in a tight and oset face-to-face stacking array in
the solid state. Because of its exible molecular framework and
dipole moment, 95.6 is moderately soluble in chlorinated
organic solvents. Time-resolved microwave conductivity
measurements conrmed that the substitution of the CC
units in 95.7 with isoelectronic BN units dramatically
enhanced hole mobility, due to the strong electronic coupling
between neighboring molecules in the solid state. The results of
CV experiments indicate that 95.6 showed an irreversible
oxidation wave and a reversible reduction wave with peak
potentials at +0.10 and 1.57 V, respectively (vs Fc/Fc+).
Reagents and conditions: (a)497 TFA, DCM, anisole, reux,

overnight, TEA, acetone; (b)498 CuI, Pd(PPh3)2Cl2, toluene, 100
C; (c)498 hydrazine monohydrate, EtOH, 100 C, pressure tube, 2 d;
(d)499 TFSIH, DCM, 30 min; (e)499 MeOH, NH3(aq), reux, 1 h.
4.2.1. Boron-Containing Azapyrenoids. BN heterapyrene systems are of interest as potential organic semiconductors
and uorescent materials (Scheme 95, for related perylenoids,
BT
Chemical Reviews
Review
Scheme 95. Synthesis of BN-Embedded Pyrenesa
both as a synthetic and as a fabrication method, resulted in a

stepwise generation of the fully conjugated BN pyrenes
95.12ab. The resulting devices showed only modest brightness and current eciencies as a result of the relatively low
photoluminescence of the BN pyrenes.
4.3. Oxa- and Thiapyrenoids
Benzo[c]phenanthro[2,1,10,9-klmn]xanthene 96.5a, containing

the 1-oxapyrene substructure, was prepared by Clar and Kelly
in 1957 starting from chrysene (Scheme 96).507 The most
straightforward although unselective route involved the Elbs
reaction performed on the acylation products obtained from
chrysene and o-toluoyl chloride. In an alternative stepwise
synthesis, proposed as a structural proof, dibenzo[a,f ]tetraphene 96.4 was assembled in three steps and oxidized to
96.5a by heating in the presence of air. In a reinvestigation of
the Elbs route, Mabille and Buu-Ho additionally obtained the
methyl derivative 96.5b, and suggested anthrols 96.7ab as
intermediates en route to 96.5ab.508 Structurally related
systems, 96.9 and 96.10, were proposed by Zander as fusion
products of 96.8 on the basis of mass spectrometric analysis.509
A dithiapyrene system 96.11 was reported by Brauer and coworkers, without providing synthetic details.182 Self-sensitized
photooxygenation of 96.11 in oxygen-saturated toluene, carried
out in the presence of sunlight, yielded the endoperoxide 96.12
with a quantum yield of 0.02. Irradiation of 96.12 at 248 nm led
to photocycloreversion accompanied by an unspecied
rearrangement process.
Quinone system 97.2, named cis-coerodioxonone by Cook
and Waddington, was obtained by condensing compound 97.1
in sulfuric acid.146 97.4 was prepared by Cooke and Dagley as a
model of the chromophore found in plant pigments isolated
from members of the Hemodoraceae family.510 The nucleophilic cyclization of the dimethoxy precursor 97.3 proved to be
more ecient than the oxidative coupling of 97.5. Interestingly,
a similar chromophore can be found in the commercial
uorescent dye, Solvent Orange 63 97.7, containing the
benzothioxanthene motif. The dye can be prepared by a
thermal cyclization of a diazonium salt derived from the
benzanthrone precursor 97.6.511
Xylindein (wood-derived indigo-like dye, 98.1, Scheme 98)
is a natural blue-green pigment found in wood infected by the
fungus Chlorociboria aeruginosa (Figure 4). This pigment was
isolated in the 1860s,512,513 but its structure was only fully
established in 2000, when Hashimoto and co-workers assigned
the absolute conguration of the substituted derivative 98.2
using X-ray diraction.514 While the total synthesis of 98.1 has
still to be accomplished, a number of derivatives containing the
xylindein chromophore have been reported. In particular, the
chiral analogue 98.5, described in 1966 by Blackburn,
Cameron, and Chan, was obtained by dimerization of the
quinone precursor 98.3, followed by acetylation of the
intermediate xylaphin 98.4.515 The unsubstituted chromophore, xantheno[2,1,9,8-klmna]xanthene-4,10-dione 98.8, was
synthesized earlier by Pummerer and co-workers by means of
Cu-mediated cyclization of 1,1-bi-2-naphthol 98.6,516 followed
by oxidation with peroxymonosulfuric acid.517 The intermediate dinaphthylene dioxide 98.7, also known as dioxaanthranthrene or peri-xanthenoxanthene (PXX),518,519 is an interesting
fused system in itself, and a range of its extended analogues
such as 98.11,520 98.12,521 or 98.13522 were subsequently
prepared. The xylindein chromophore was also obtained in an
unexpected rearrangement of the dinaphthofuran 98.9, which
Reagents and conditions: (a)503 (1) toluene, 3 days, rt, (2) PtCl2,
toluene, 36 h, 95 C; (b)503 toluene, 48 h, rt; (c)503 PtCl2, toluene, 24
h, 95 C; (d)505 4 mol % Pd(dba)2, 4 mol % P(t-Bu)3, t-BuONa,
toluene, 10 h, 100 C; (e)505 (1) BuLi, toluene, 1 h, 78 C, (2) 1 h, 0
C, (2) BCl 3 , 78 C, (3) 8 h, rt, (4) AlCl 3 , 2,2,6,6tetramethylpiperidine, 1,2-dichlorobenzene, 0 C, (5) 12 h, 150 C;
(f)506 exciton-driven elimination.
While the electrochemical HOMOLUMO gap (1.67 eV) in

95.6 was smaller than that in pentacene (2.09 eV), no obvious
decomposition was observed, even at the melting point (358
C) under atmospheric conditions.
In 2015, Wang and co-workers reported a double arene
elimination from the BN-pyrene precursors 95.10ab, induced
electrically within electroluminescent devices by means of
exciton-driven elimination.506 This process, which is of interest
BU
Chemical Reviews
Review
Scheme 96. Synthesis of Oxapyrenoidsa
Reagents and conditions: (a)507 AlCl3, phthalic anhydride, tetrachloroethane, 90 C; (b) (1) benzyl chloride, reux, (2) H2SO4 (conc.), (3) 10 min,
reux; (c) zinc dust, pyridine, 80% AcOH, 5 h, reux; (d) heating above melting point; (e) (1) AlCl3, o-toluoyl chloride, tetrachloroethane, 9 min, 95
C, (2) pyrolysis, 15 min, 400 C; (f)508 (1) AlCl3, o-toluoyl chloride or 2,2-dimethylbenzoyl chloride, dry carbon disulde, 10 min to 22 h, rt, (2)
13 h, reux; (g) 30 min, reux; (h) pyrolysis, 15 min, 400 C; (i)509 Zn dust.
a
Scheme 97. Oxa- and Thiapyrene Ketonesa
Reagents and conditions: (a)146 75% H2SO4, 6 h, 170 C; (b)510 HBr, 45% AcOH, reux; (c) VOF3, triuoroacetic acid; (d)511 (1) nitrosylsulfuric
acid, 10 to 0 C, mixed pyridine solvent, (2) reux, 3 h.
a
In 2013, Bucher, Cronin, et al. reported the synthesis of the

naphthoxanthenyl radical 101.5, which may be viewed as a
resonance-stabilized phenalenyl species (Scheme 101).528 The
radical could be obtained by NaI-mediated reduction of the
naphtho[2,1,8-mna]xanthenium cation 101.2, which was itself
prepared in two steps from phenalenone. Alternatively, the
101.5 radical could be photochemically generated from 9phenylphenalen-1-one 101.3 in the presence of TCNE as the
oxidant. The radical showed an ESR spectrum with wellresolved couplings to 11 protons, and was found to absorb light
up to ca. 700 nm. Electrochemical reduction of 101.2 to 101.5
was associated with a potential of 0.52 V (vs Fc/Fc+), whereas
an additional reduction at 1.66 V corresponded to the
formation of an anion. In subsequent work from the Bucher
group, two isomeric extended cations 101.67 were prepared,
along with the corresponding radicals 101.89.529 First
reduction potentials of 101.6 and 101.7 were, respectively,
higher (0.43 V) and lower (0.59 V) than the potential
measured for 101.2, indicating a dierence in -conjugation
eects. Unexpectedly, 101.7 showed the most red-shifted
optical absorption in comparison with other systems. The
strong yellow uorescence of 101.7, combined with high
was converted into the tetramethoxy derivative 98.10 under the

action of vanadyl triuoride in TFA.523 The absorption
spectrum of 98.10 is strikingly similar to that of xylindein.
An example of a -extended carbocyanine dye 99.4
containing 1,3-thiazine rings was reported in 1961 by
Neunhoeer and Weigel (Scheme 99).525 Their synthesis
consisted of an oxidative cyclization of thioacetamide 99.1
followed by quaternization and condensation with triethyl
orthoformate. The resulting 99.4 dye showed strong
absorbance with max = 565 nm.
A thioxanthene system 100.2 was synthesized in 2014 by Liu,
Li, et al., using an acid-mediated ring closure followed by
nucleophilic demethylation (Scheme 100).526 In comparison
with its ortho-fused isomers (107.9 and 107.11, section 4.5),
compound 100.2 exhibited the most pronounced spectral redshift and highest uorescence quantum yield as well as the
largest OFET mobilities. In the same year, Zhang and coworkers prepared a series of sulfur-bridged polycycles using
oxidative double C(sp2)H activation.527 The pyrene product
100.4 was subsequently reduced to 100.5, which contained a
ring system isomeric to 100.2. Compound 100.5 showed a
uorescence quantum yield of 0.48, and exhibited good thermal
and oxidative stability in air.
BV
Chemical Reviews
Review
Scheme 98. Xylindein and Its Analoguesa
Reagents and conditions: (a)515 naphthalene-2,3-diol, phosphate buer of pH 6.6, N2 atm, 12 h, rt; (b) CH3COONa, (CH3CO)2O, Zn dust, 2 h,
reux; (c)516 (CH3COO)2Cu, 8% caustic soda, H2O, 2 h, 280290 C; (d)517 (1) H2SO4, H2SO5, ice, H2O, 24 h, rt, (2) H2SO4, ice, 24 h, rt, (3)
H2SO4, H2O; (e)523 TFA, VOF3, 15 h, rt.
Scheme 99. PyrenothiazineCarbocyanine Dyea
Reagents and conditions:525 (a) K3Fe(CN)6, KOH, MeOH, H2O;

(b) TsOMe, 140150 C, 30 min; (c) HC(OEt)3, pyridine, reux, 45
min.
chemical stability and good solubility in water, is of interest in

the context of DNA intercalation studies.
4.4. [cd]-Heterofused Pyrenoids
Pyrenes containing a [cd]annulated six-membered hetero ring

are also classiable as heteraperylenes (which is our preferred
choice) and have been discussed in the preceding section.
[cd]Annulation of ve- or seven-membered heterocycles is
relatively rare, presumably because of the associated internal
strain. Examples of such systems have already been discussed as
Figure 4. Chlorociboria aeruginosa and its growth on wood. Reprinted

from ref 524. Public Domain.
BW
Chemical Reviews
Review
Scheme 100. Thiopyran-Fused Pyrenesa
Scheme 102. Synthesis of Thiophene-Fused Pyrene

Derivativesa
a
Reagents and conditions: (a)530 NBS, THF, chloroform, overnight;
(b) (1) FeCl3, CH3NO2/dichloroethane (1:10), 2 h, (2) MeOH, 30
min; (c) (1) 1.6 M n-BuLi, THF, N2 atm, 78 C, 2 h, (2) MeOH,
78 C to rt.
Reagents and conditions: (a)526 (1) CF3SO3H, DCM, 24 h, rt, (2)

waterpyridine (8:1), 30 min, reux; (b)527 PdCl2, AgOAc,
iodobenzene, AcOH, 1,1,2,2-tetrachloroethane, 48 h, 100 C; (c)
NiCl26H2O, Al powder, THF, 0 C.
bromine substituents in 102.2b led to a markedly improved

coupling yield. The resulting 102.3ab were debrominated
using n-BuLi, to yield the Br-free product 102.4. 102.4 showed
a signicantly red-shifted absorption spectrum (max = 484 nm),
in line with its reduced HOMOLUMO gap, but it showed
relatively low hole mobility in OFET devices.
Scheme 101. Naphthoxanthenyl Radical and Related

Systemsa
4.5. [a]-Heterofused Pyrenoids
4.5.1. Direct Pyrrole Fusion. The pyrrole ring can be

fused to the [a] edge of pyrene in three distinct ways. First
examples of simple pyrenopyrroles were provided by Saint-Ruf
et al. in 1972. In that work, two phenaleno[1,9-fg]indoles
103.1ab were prepared via the MohlauBischler synthesis as
potentially carcinogenic analogues of benzo[a]pyrene (Scheme
103).531 In 2004, Fang, Chou, et al. reported the synthesis of
the isomeric phenaleno[1,9-ef ]indole 103.4 via the HemetsbergerKnittel synthesis, followed by ester group removal.532
103.4 and related derivatives were uorescent with maxem up to
438 nm and quantum yields reaching 0.96. 103.4 was further
transformed into the bipyrrole 103.6 and the bis-phenalenefused indigo 103.7, using, respectively, Stille coupling and
cumyl hydroperoxide-mediated coupling. 103.6 showed strong,
bathochromically shifted uorescence (maxem = 482, F =
0.50). In the indigoid product 103.7, the red shift was
considerably larger (maxabs = 687, maxem = 707), at an expense
of considerable reduction of quantum yield (F = 0.0076). In
later work, it was shown by the same group that 103.6 acted as
a selective uoride sensor, switching from green to red
uorescence when treated with NBu 4 F in a DMSO
solution.533,534 The eect was shown to be caused by the
deprotonation of the bipyrrole caused by the basic uoride
anion, resulting in the formation of the highly colored anion
103.8. A pyrenopyrrolenaphthyridine guanine sensor 103.9,
containing the 103.4 unit, was also developed by Fang et al.,
providing uorescence detection in the visible region.535
In 2009, Castanheira, Ferreira, et al. showed that the Bocprotected enamine 103.10 underwent a Pd/Cu-mediated
cyclization to the pyrrole-fused product 103.11 in moderate
yield.536 The proposed mechanism of this reaction involves a
double electrophilic attack of PdII on the 2 position of pyrene
and the enamine nitrogen, followed by reductive elimination of
Pd0 and reoxidation to PdII with the copper salt. A Ru-catalyzed
synthesis of (Z)-3-methyleneisoindolin-1-ones from nitriles and
vinyl sulfones or acrylates, described in 2014 by Reddy and
a
Reagents and conditions:528 (a) (1) 2-methoxyphenylmagnesium
bromide, THF, (2) DDQ, DCM; (b) (1) BBr3, DCM, (2) H2O,
HBF4; (c) NaI, DMSO, or MeCN; (d) h, TCNE.
intermediates in the synthesis of larger fused frameworks (e.g.,

47.2 or 34.6). An unusual example of highly annulated pyrene
derivative was provided in 2012 by Yu, Wong, Liu, et al., in
their report on -extended buttery-shaped heteroarenes.530
Their work included the synthesis of the peri-fused molecule
102.4, containing the pyreno[1,2-b:8,7-b:4,3-bc:5,6-bc]tetrathiophene ring system (Scheme 102). The key step
involved oxidative coupling of brominated precursors
102.2ab, which resulted in the formation of direct
thiophenethiophene bonds. Increasing the number of
BX
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Scheme 103. Pyrenopyrrolesa
Reagents and conditions: (a)532 toluene, 110 C, 4 h, 92%; (b)532 (1) KOH, THF, H2O, reux, 2 h, 97%, (2) Cu, quinoline, 220 C, 2 h, 91%;
(c)532 Boc2O, cat. DMAP, THF, 25 C, 5 h, 99%; (d)532 (1) t-BuLi, THF, (2) Bu3SnCl, 78 C, 2 h; (e)532 (1) t-BuLi, THF, (2) I2, 78 C, 2 h;
(f)532 cat. Pd(PPh3)2Cl2, DMF, 110 C, 5 h; (g)532 cumyl hydroperoxide, cumene, cat. Mo(CO)6, benzoic acid, 80 C, 5 h; (h)533,534 [NBu4]F,
DMSO; (i)536 Pd(OAc)2 (50 mol %), Cu(OAc)2 (3 equiv), DMF, 160 C, 34 h, Ar; (j)537 [{RuCl2(p-cymene)}2], AgSbF6, Cu(OAc)2H2O,
AcOH, 120 C, 60 h; (k)538 [Cp*RhCl2]2, Ag2CO3, DMF, 70 C, 40 h.
a
Scheme 104. Synthesis of Phenaleno[1,9-gh]quinolinea
Jeganmohan, was successfully used for the preparation of more

extended fused frameworks, notably the highly uorescent
pyrene derivative 103.13.537 Substituted phenaleno[1,9-fg]indole 103.15 was prepared in 2014 by Jin et al., using the
newly developed oxidative annulation of alkynes to N-aryl
carbamates.538 -Extended carbazole derivatives, including
pyrene-containing systems 103.1617, were obtained via
FeCl3-mediated oxidative coupling by Kumar and Tao.539
The coupling was ecient (yields >60% for 103.17), even
though the activating methoxy substituents were located meta
(rather than para or ortho) to the expected coupling sites.
4.5.2. Other N-Containing Systems. Phenaleno[1,9gh]quinoline 104.2 (pyrenoline) was synthesized by Jahoda
as early as 1887, by using the Skraup reaction (Scheme 104).540
In 1937, Vollmann et al. described a moderately selective
oxidation of pyrenoline to the corresponding dione 104.3.541
Much of the subsequent interest in [a]fused pyrene derivatives
was motivated by research on aromatic carcinogens and
potential tumor inhibitors. Some of these systems, such as
105.3, were made with fused heterocyclic subunits. The
synthesis of 105.3, reported in 1958 by Saint-Ruf, Buu-Ho,
and Jacquignon, consisted of Fischer indolization performed on
the quinone 105.1, followed by dehydrogenation with
Reagents and conditions: (a)540 nitrobenzene, glycerin, H2SO4,

reux; (b)541 CrO3/AcOH.
chloranil.542 Thummel and co-workers used a similar strategy

for the preparation of 105.4 and 105.5.543 These two
compounds, which were not dehydrogenated further, were
used as cyclometalating ligands for ruthenium(II). A dierent
route to pyrene [a]fusion was taken in 2008 by Klumpp and coworkers in their exploration of superelectrophilic cyclizations.544 The pyridine-substituted precursor 105.7, available
in two steps from pyren-1-ylboronic acid 105.6, was treated
with triuoromethanesulfonic acid, yielding the isoquinoxaline
product 105.8, in which the electrophilic ring closure occurred
with the elimination of a benzene molecule. In their work on
multiply arylated pyrenes, reported in 2015, He and Zhong
BY
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Khan et al.547). The Martinet reaction was used to prepare the

pyrenoisatin derivative 106.5, which was further reacted with ophenylenediamine to yield 106.6. Compound 106.7 was
obtained from 106.1 in the ConradLimpach reaction. In
subsequent work, a thiophene-fused system 106.8 was
reported.548
4.5.3. Other Five-Membered Rings. [a]Fusion of other
ve-membered rings was explored to a limited extent.
Pyreno[1,2-c]furan 107.1 was synthesized in 1988 by
Moursounidis and Wege,549 using their cycloaddition/cycloreversion method, described in more detail below (Scheme 119,
section 4.7). The other two isomeric pyrenofurans 107.23
were obtained in 1985 by Royer and co-workers via
intramolecular aldol-type condensations.550 Dipyreno[1,2b:2,1-d]furan 107.6 and its quinone derivatives were reported
by Chesnovskii et al., as products of acid-catalyzed
condensation of 1,6-pyrenequinone.551 A four-step synthesis
of pyreno[2,1-d]isoxazole 107.4 from pyren-1-ol was described
by the Rebek group.552 The closure of the isoxazole ring was
achieved using a newly discovered TsCl/i-Pr2NEt cyclization. 8Methylpyreno[2,1-d]thiazole 107.5 was obtained in 1961 by
Neunhoeer and Weigel by oxidative cyclization of 2thioacetaminopyrene, and used for the synthesis of carbocyanine dyes 107.7.553
Two isomeric benzothiophene-fused pyrenes 107.9 and
107.11 were synthesized by Liu, Li, and co-workers in 2014
(Scheme 107).526 These compounds were obtained from
sulfoxides 107.8 and 107.10, respectively, which were subjected
to the cyclizationdemethylation sequence described earlier for
100.2. Pyreno[1,2-b]thiophene 107.14 was rst reported in
1958 by Pandya and Tilak as a product of acid-catalyzed
cyclization of (2,2-dimethoxyethyl)(pyren-1-yl)sulfane
107.15.554 A two-step synthesis of thiophene end-capped
aromatics, developed in 2012 by Thongpanchang et al.,
provided an alternative route to 107.14.555 The compound
was prepared by condensing pyren-1-ol 107.12 with 2mercaptoethanol, and subsequent dehydrogenation with
chloranil. The isomeric 107.23 was obtained in 1981 by Castle
et al.556 This synthesis was considerably more complex,
requiring consecutive closure of two benzene rings.
synthesized the disubstituted derivative 105.9, which was

subjected to a range of oxidative cyclization conditions.545
While FeCl3- and DDQ-mediated oxidations were ineective,
potassium metal was found to induce ecient coupling, leading
to the isoquinoline product 105.10 (Scheme 105).
Scheme 105. Synthesis of Nitrogen-Containing [a]Fused
Pyrenoidsa
4.6. Pyrazacenes
a
4.6.1. Pyrazine-Fused Systems. The availability of

pyrene-4,5-dione and pyrene-4,5,9,10-tetraone building blocks
(108.1 and 108.3, Scheme 108) provides access to diverse
pyrazine-fused pyrenoids. Large molecular structures of this
kind (pyrazacenes) have been developed as potential organic
materials, as recently reviewed by Mateo-Alonso.351 First
examples of this chemistry were reported in the comprehensive
1937 paper by Vollmann and co-workers, who synthesized the
quinoxaline derivatives 108.2 and 108.4, which can be seen
respectively as benzo-fused 5,12-diazatetracene and 5,8,13,16tetraazahexacene.541 These two systems illustrate the underlying structural paradigm, which enables the assembly of 2nazaacenes of considerable length and remarkable chemical
stability.
The diketonediamine reactivity was soon found to be
general and usable with variously substituted diamines557 and
pyrenoquinones.558 Similar reactions with diaminomaleonitrile,
reported in 1975 by Wohrle et al., yielded cyano-substituted
C24.1 and C24.2a (Chart 24).559 The latter species was used
to show the dependence of nitrile group fragmentation in mass
spectrometry on the aromaticity of the cyclic system.560
542
Reagents and conditions: (a)

phenylhydrazine, HCl in
CH3COOH; (b) chloranil, xylene; (c)543 2-aminobenzaldehyde,
KOH, absolute EtOH, under Ar atm, 12 h, reux; (d)544 (1) 3bromoisonicotinaldehyde, K3PO4, 5 mol % Pd(OAc)2, 1,4-dioxane,
overnight, reux, (2) benzyltriphenylphosphonium bromide, n-BuLi,
THF, 2 h, 78 C, (3) aldehyde obtained in step 1, 4 h, 25 C; (e)
CF3SO3H, chloroform, 4 h, rt; (f)545 K, dry toluene, 24 h, 125 C.
Using 1-aminoperylene 106.1 as the starting material, the

group of Buu-Ho prepared a series of pyrenes with ortho-fused
heteroaromatic rings (Scheme 106).546 Benzoquinoline-fused
derivatives 106.3a and 106.4a were obtained by reuxing 106.1
with paraformaldehyde and - or -naphthol, respectively.
106.2a or 106.2b, synthesized from 106.1 and - or naphthol, were converted into the methyl analogues 106.3b
and 106.4b by condensation in acetic acid. Alternatively,
condensation reactions of 106.2a or 106.2b with arsenic
trichloride or sulfur and iodine produced, respectively, arsazines
106.910 and thiaazines 106.1112 (for another sulfurcontaining derivative, thioxanthenone 106.13, see the work by
BZ
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Scheme 106. Synthesis of Heteroaromatic [a]Fused Pyrenoids from 1-Aminoperylenea
a
Reagents and conditions: (a)546 -naphthol, iodine, 36 h, 250 C; (b) -naphthol, iodine, 36 h, 250 C; (c) -naphthol, paraformaldehyde, reux;
(d) -naphthol, paraformaldehyde, reux; (e) ZnCl2 (anhydrous), acetic anhydride, 24 h, reux; (f) diethyl mesoxalate, CH3COOH, 1 h, reux; (g)
o-phenylenediamine; (h) (1) ethyl acetoactate, piperidine, EtOH, 24 h, reux, (2) Zn powder, distillation; (i)548 benzo[b]thiophen-3-ol,
paraformaldehyde.
Scheme 107. Thiophene-Fused Pyrenesa
a
Reagents and conditions: (a)526 (1) CF3SO3H, 24 h, rt, (2) waterpyridine, 30 min, reux; (b)555 2-mercaptoethanol, TFA, chlorobenzene, 3 h,
reux; (c)555 chloranil; (d)554 PPA; (e)556 NaH, DME; (f)556 I2, cyclohexane, medium pressure Hg lamp; (g)556 NBS, benzoyl peroxide, benzene,
reux; (h)556 KCN, benzene, water, Aliquat-336, reux; (i)556 DIBAL-H, toluene, benzene, rt; (j)556 PPA, steam bath.
bright blue uorescence and three-step reversible reduction

potentials,562 whereas two reversible reduction waves, with a
LUMO level of 3.6 eV, were observed for C24.2c.563 C24.4,
reported by Bunz, Hamburger, and co-workers, showed
Alternative reaction conditions were reported in 2012 by Wang,

Zhi, et al., who used C24.2a for the synthesis of twodimensional zinc phthalocyanine polymers.561 The tert-butyl
derivative C24.2b, synthesized in a similar manner, exhibited
CA
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absorption spectra and theoretical calculations. A pyrene-fused

phenazinothiadiazole C24.7 with enhanced electron mobility in
FET devices (0.016 cm2 V1 s1) was described in 2015 by
Mateo-Alonso, Sun, et al.568
Pyrenepyrazine hybrids were explored as ligands by several
groups. Ishow and Gourdon prepared and characterized a
mixed-ligand ruthenium complex C25.1 (Chart 25) along with
its dinuclear analogue (Chart 30).569 Compound C25.1 was
obtained by heating {[Ru(bpy)2(5,6-diamino-1,10-phenanthroline)](PF6)22H2O} with tetraketone 108.1 in acetonitrile.570
Gao, Chao, Ji, et al. prepared closely related systems C25.2ab
by reacting bis(bipyridyl) Ru complexes with a preassembled
phenazine ligand.571 Both complexes intercalated into DNA
base pairs with very high anity even at high salt
concentrations. The complexes were able to eectively inhibit
DNA transcription activity by blocking the binding of T7 RNA
polymerase to the template DNA. Barton and co-workers used
C25.2a for targeting DNA defects, investigating the luminescent response to base-pair mismatches and/or abasic sites.572 A
related structural design, C25.3, was used by Ruan and coworkers as a uorescent sensor.573 Compound C25.3 exhibited
a selective uorescence-quenching response to Hg2+ in aqueous
acetonitrile solution, and its detection limit was lower than the
toxic level of Hg2+.
The crown ether C25.4b574 and its smaller analogue C25.4a
were explored as cation sensors by Al-Sayah, Kaafarani, et al.575
NMR investigations showed that C25.4a formed 1:1 complexes
with small ions (sodium and calcium) and 1:2 complexes with
large ions (potassium, rubidium, cesium, and barium) as
evidenced by the changes of chemical shifts. Sensor C25.4b
showed weak binding with small monovalent ions (Li and Na),
but it formed 1:1 complexes with Ca2+, K+, and Ba2+. Similar
investigations were performed on the bis(crown ethers)
C25.5b576 and C25.5a,575 revealing strong binding to Ba and
Ca ions.
Diazapentacene systems containing a single pyrene substructure were reported by several research groups (Scheme
109). Compound 109.1a, prepared in 2007 by Mateo-Alonso,
Guldi, Prato, and co-workers, was shown to promote dispersion
of SWCNTs in THF.577 Photophysical experiments indicated
that the dispersion was induced solely by interactions. The
TIPS-ethynyl-substituted derivative 109.1b, investigated by
Bunz, Hamburger, et al., exhibited a pyrene-induced red-shift
Scheme 108. Synthesis of Pyrazine-Fused Perylenes from

Perylenoquinonesa
Reagents and conditions: (a)541 o-phenylenediamine, AcOH, reux.
markedly red-shifted absorption (max = 458 nm) and emission

(max = 461 nm) relative to the less extensively fused analogues,
but its OLED performance was not tested.564 Compounds
C24.3 (Chart 24) and 110.2b (Scheme 110) also prepared by
direct condensations of appropriate amines, were used as anion
sensors by Al-Sayah, Kaafarani, et al.565 C24.3 exhibited high
anity to acetate, benzoate, cyanide, and uoride ions, yielding
pronounced changes in absorption spectra and 1:1 sensor-toanion binding ratios. A similar binding capability was observed
for 110.2b, which yielded a sensor-to-anion ratio of 1:2.
In 2014, Lin, Cui, and co-workers prepared a series of fused
5,12-diazatetracenes C24.5ah containing dierent terminal
aromatic units.566 Compounds C24.5ab were prepared using
the conventional condensation protocol, and the aromatic units
were attached to C24.5b using Suzuki and Sonogashira
reactions. C24.5ah displayed moderate to strong uorescence, with quantum yields of 0.100.60 and emission maxima
occurring typically in the 470480 range (DCM solution, 640
nm for C24.5h). A TTF-containing donoracceptor system
C24.6 was developed in 2011 by Jia and co-workers.567 The
observed increase in the oxidation potentials of C24.6 relative
to the TTF reference suggested a good electronic communication between the donor and acceptor. Evidence for
intramolecular charge transfer (ICT) in compound C24.6,
arising from a HOMOLUMO transition, was obtained from
Chart 24. Pyrazine-Fused Pyrenoids
CB
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Chart 25. PyrenePyrazine Hybrids as Ligands
similar to that of its smaller analogue C24.4.564 The nitrilesubstituted molecule 109.2 was synthesized by the Lee group as
a reference system for comparison with electron-decient
pyrazineacenes (see Chart 26).578 109.3 was obtained as an
intermediate used for the synthesis of the extended acene
C31.8 (Chart 31).579
The synthesis of the diazapentacene 109.4, reported in 2012
by Sun, Zhang, et al., relied on a dionediamine conversion
sequence, consisting of dioxime formation and subsequent
reduction (109.5 to 109.7, Scheme 109).580 109.5 was then
condensed with diamine 109.7, producing 109.4 in 30% yield.
109.4 possessed two absorption peaks centered at 350 and 460
nm with a shoulder at 434 nm, corresponding to an optical
bandgap of 2.69 eV. The compound exhibited bright green
uorescence with an emission maximum at 481 nm. The UV/
vis absorption and the solution color of 109.4 could be changed
by adding a Lewis acid or a strong protic acid.
Following the synthesis of the parent tetraazahexacene
system 108.4, discussed above, a number of its substituted
derivatives have subsequently been reported, such as 110.1a581
and 110.1b582 (Scheme 110). The latter species was shown by
Gigmes, Lalevee, and co-workers to be an ecient polymerization photoinitiator.582 108.4 and 110.1b were employed in
bottom-gate p-channel organic thin-lm transistors, showing
eld-eect mobilities of 2.5 103 and 7.5 105 cm2/Vs in
ambient air.583
By condensing tetraone 108.3 with benzene-1,2,4,5-tetraamine, Stille and Mainen synthesized the ladder polyquinoxaline polymer 110.7.71,72 Interestingly, this polymer (with an
estimated molecular weight of ca. 7000) showed partial
solubility in HMPA, and its thermal stability under nitrogen
(up to 700 C) was improved relative to nonladder analogues,
such as the pyrene-containing 110.8. The work on 110.7,
published in the 1960s, apparently constitutes the rst attempt
to synthesize heteroatom-doped graphitic nanoribbons (for a
related coronenoid nanoribbon, see Scheme 8, section 2.1).
Following Stilles reports, a related modular approach was
explored by Arnold584,585 and Hedberg et al.586 Compound
110.2a, obtained by reacting 108.3 with 1,2-diamino-4,5-(ptoluenesulfonamido)benzene, was detosylated to provide
110.2c. The latter tetraamine was condensed with naphthalene-1,4,5,8-tetracarboxylic acid, pyromellitic anhydride, or the
Scheme 109. Diazapentacenesa
Reagents and conditions: (a)580 NH2OHHCl, pyridine, EtOH, 24 h,

reux; (b) (1) SnCl2, HCl conc., EtOH, 0 C, (2) overnight, reux;
(c) 109.5, AcOH, triuoroacetic acid, 2 days, reux.
double benzil 110.6, yielding polymers 110.35, respectively.

The formation of imidazole or pyrazine linkages in these
polymers was most likely nonregioregular. The thermal
properties of the ladder-type polymers 110.34 were
comparable to those of 110.7.
Functionalized tetraazahexacenes bearing mesogenic alkoxy
and alkylthio substituents were explored by several groups
(Scheme 111). A series of tetraalkoxy derivatives, including
systems 111.4df, were reported in 2004 by Harris and coworkers.587 111.4d was shown to form a liquid crystalline phase
CC
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Scheme 110. Pyrene-Containing Tetraazahexacenes and Related Polymersa
Reagents and conditions: (a)71,72 (1) conc. H2SO4, rt, (2) 20% ammonium carbonate, 65%; (b) PPA, N2, 180 C; (c)586 m-cresol, 120 C, 18 h.
Scheme 111. Synthetic Route to Pyrene [e]Fused Hexaacenesa
Reagents and conditions: (a)592 4,5-dichloro-1,2-phenylenediamine, EtOH:AcOH (1:1), 24 h, reux; (b)589,592 K2CO3, alkylthiol, DMF, Ar atm, 1
week, 80 C; (c)587,594 4,5-dialkoxy-1,2-phenylenediamine, EtOH:AcOH 1:1, Ar atm, 24 h, reux.
in the broadest temperature range (213268 C), in contrast

to 111.4ef, which were nonmesomorphic. The roomtemperature structure of 111.4d was determined to be a
crystalline phase with orthogonal symmetry, in which the stacked cores were tilted relative to the columnar axis.588 At
235 C, the LC phase of 111.4d was found to be of the Colr
type, with C2/m planar symmetry. Columnar phases were also
identied for other substituted derivatives, such as 111.4 g.588
Alkylthio derivatives 111.3ad were prepared in 2007 by
Kaafarani, Jabbour, et al. in a two-step synthetic procedure,
consisting of pyrazine cyclization and thiolate substitution.589
These systems turned out to be nonmesogenic, although
multiple crystal-to-crystal transitions were observed for

111.3a.590 With estimated HOMO and LUMO energy levels
of 5.57 and 2.97 eV, respectively, these compounds were
investigated as potential semiconductor materials for organic
electronics. An OFET device based on 111.3a showed pchannel characteristics, with an average saturation hole mobility
of 103 cm2 V1 s1.589 In thin lms, the 111.3a molecules are
arranged within layers, and the aromatic cores are separated
from the alkane side chains.591 Both the core long axes and the
side chains were found to be highly tilted with respect to the
surface normal, with cofacial packing of the core units. The
columnar mesomorphism of 111.3eh was subsequently
CD
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Chart 26. Unsymmetrically Substituted Hexacenes578,596598
investigated by Eichhorn, Kaafarani, et al.592 They showed that

lateral extension of the core to cruciform structures (as in
111.3gh) was essential for the formation of hexagonal
columnar mesophases, while the incorporation of phytanyl
side-chains, although not mesogenic by itself, is most eective
in the control of phase transition temperatures.
In 2010, Valentini, Kaafarani, and co-workers described the
morphological and electronic properties of 111.3d combined
with butylamine-modied graphene sheets.593 The lm
deposited from the butylamine-modied graphene sheets/
111.3d blend showed a photoelectrical response higher than
those prepared with neat 111.3d or with unmodied graphene
blends. Fused tetraazahexacenes showed photoluminescent
behavior resembling that of pyrene. Concentration-dependent
uorescence measurements performed for 111.3ab and
111.4cd showed the formation of excimers even at nanomolar
concentrations.594 The observed variation of the Stokes shift,
uorescence quantum yield, and uorescence lifetime was
found to correlate with the number of carbons in the alkyl
chain.595
Stepwise condensations provide access to unsymmetrically
substituted hexacenes. In 2008, Lee and co-workers used this
strategy to prepare compounds C26.1a,e,g (Chart 26).596 All of
these materials were observed to form organogels through the
growth of nanobers via a cooperative interplay of
stacking, hydrogen bonding, and van der Waals interactions.
Compound C26.1g exhibited acid-sensing abilities in the
xerogel lm. In subsequent work from the Lee group,
compounds C26.1a,b,eg and C26.2 were investigated as
self-assembling n-type organic semiconductors, with substituent-dependent properties.597 Among the substituents studied,
the nitro group (C26.1f and C26.2) gave the most pronounced
lowering of the LUMO energy level (by 0.6 eV), and the
narrowest HOMOLUMO gap, when compared to C26.1a.
Signicant inuence of these peripheral substituents was also
observed in the morphology of self-assembled structures. Even
with dierent types of peripheral substituents, the ability to
produce 1D nanostructures was largely maintained. In addition,
the length of alkoxy group, assembly method, and assembly
conditions inuenced the ber morphology signicantly. In a
subsequent report, compounds C26.1ad,f and C26.3
containing F, Cl, Br, and NO2 substituents were described.598
It was found that LUMO levels were lowered more signicantly
in compounds containing Cl and Br than in the F-substituted
derivatives.
Terminal aryl substitution in linear pyrazacenes was reported

in 2008 by Wang and co-workers, enabling the preparation of
hexacenes C27.1ac (Chart 27), as well as more extended
Chart 27. Aryl-Substituted Fused Tetraazahexacenes
oligomeric tapes (C33.14, Chart 33).599 Further examples

were provided in 2013 by Kaafarani, Eichhorn, et al., who
prepared octaalkoxy derivatives C27.2 and C27.3, by direct
condensations of respective ortho-terphenyl and triphenylenediamines.600 Attempted oxidative coupling of compound C27.2
to C27.3 was unsuccessful. Both compounds displayed several
types of uorescent columnar mesophases over wide temperature ranges.
Self-assembly and electronic properties of ethynyl-substituted
systems C28.23 were explored by Lee and co-workers (Chart
28).601 All of these systems were derived from the dibromosubstituted C28.1 by using Sonogashira reactions. Placing
dierent functional groups (OCH3, H, CN) on the ethynyl
arms of C28.3ac progressively reduced LUMO energies, as
predicted by theoretical calculations and experimentally veried
by cyclic voltammetry (CV). Furthermore, the morphologies of
1D assembly were greatly inuenced by the substituents. While
the conformational exibility of OCH3 groups hampered
successful assembly, hydrogen and cyano substitution induced
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Chart 28. Asymmetrically Substituted Pyrene-[e]Fused Hexaacenes
Chart 29. Tetraazahexacene-Based Polymers
formation of the nanobers, while interactions are

dominant for the straight strands.
Another class of self-assembling derivatives, C28.4ae,
showed the eect of the position, type, and number of
peripheral substituents on the optical and electrochemical
properties of the entire system.603 For these systems,
organogelation was also observed, including a thixotropic
behavior, which originated from extensive three-dimensional
entanglement of the bers. The substitution showed a
the formation of rigid microstrands and exible nanobers,

respectively. Self-assembly of C28.3c using a phase transfer
method showed morphological transformation from straight
strands to exible nanobers with signicant bundling and
coiling, and nally at nanobers with less bundling as solution
concentration increased.602 X-ray diraction and FT-IR spectroscopy of the assembled structures showed that intermolecular cyano interactions are the major driving force for the
CF
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signicant inuence on the morphology of the bers formed

through organogelation, with dodecyl chains providing higher
gelation temperatures than hexadecyl chains. The position of
the peripheral substituents inuenced the ber morphology by
modulating the intermolecular CN (or CHO) interactions and
stacking. In contrast to CN-substituted derivatives,
compounds with CHO groups formed islands of ber
aggregates.
Tuning of HOMO and LUMO energies via terminal fusion
of aromatic -extender rings to pyrenepyrazine hybrids was
explored in 2013 by Lee and co-workers.578 -Extended
derivatives containing pyridine (C26.4), pyrazine (C26.5),
and benzothiadiazole (C28.5a and C28.5b) were prepared, and
their properties were compared to those of the dicyano
reference 109.2. It was found that the imine function was
comparable to the nitrile substituent in its LUMO-lowering
ability, with the strongest eect being observed for the
dibromobenzothiadiazole-fused C28.5a. In all cases, the
HOMO energy was negligibly aected. Thiophene-containing
donoracceptor systems C28.5c and C28.6 were also
prepared, with the former showing a HOMOLUMO gap of
1.55 eV.604 This compound self-assembled into bers with a
100200 nm width, composed of nanotapes ca. 10 nm wide.
Conjugated copolymers C29.2ad and the reference
molecule C29.1, all based on 9,9-dioctyluorene and arylsubstituted hexacene subunits, described above, were synthesized in 2010 by Wang and co-workers using Suzuki coupling
(Chart 29).605 A range of polymer compositions were obtained,
wherein the molar fraction x of the hexacene component varied
from 0.01 to 0.20. Energy transfer from the conjugated main
chain to the hexacene moieties was observed using uorescence
spectroscopy. Full energy transfer was achieved when the molar
content of the hexacene was 0.20 (C29.2d, toluene solution).
In the thin lm, complete energy transfer was observed even for
the C29.2a copolymer. The LUMO energy levels of the
copolymers (3.06 eV) were lower than those of the
polyuorene homopolymer (2.65 eV), indicating that the
introduction of the hexacene unit was benecial for electron
injection. Single-layer electroluminescent devices (ITO/PEDOT:PSS/polymer/LiF/Al) were fabricated, and showed
better maximum brightness and current eciency than the
homopolymer. The best single-layer device was based on
C29.2b, with a maximum brightness of 1532 cd/m2 and current
eciency of 1.09 cd/A. Much higher eciency could be
achieved for multilayer EL devices of C29.2b (ITO/
PEDOT:PSS/PVK/polymer/TPBI/LiF/Al), which showed a
maximum current eciency of 10.01 cd/A. In subsequent work
from Wang and co-workers, analogous copolymers C29.4ad
were prepared, with uorene chains attached to the pyrene
core.606 Compound C29.3a was used to synthesize the
copolymers and the reference system C29.3b, using Suzuki
coupling. A single-layer PLED device based on C29.4c
provided a maximum brightness of 485 cd/m2, a current
eciency of 0.29 cd/A, and an external quantum eciency of
0.10%. These parameters could be considerably improved in
multilayer devices. In 2015, highly porous imidazole-linked
polymers C29.5 and C29.6 were reported by Arachchige,
Kaafarani, El-Kaderi, et al.607 Their synthesis involved
condensations of the tetraamine 110.2d with appropriate
branched tetraaldehydes, which produced the highly crosslinked structures in 7479% yields. These materials had a high
surface area (SABET = 950 m2 g1), revealing bandgaps in the
semiconducting range (2.02 and 2.16 eV) and luminescence
emission in the orangered region of the spectrum (600 and

630 nm).
In 1998, Gourdon et al. prepared a dinuclear ruthenium
complex C30.1 containing a pyrazacene bridging ligand.569
Compound C30.1 was obtained in a reaction between
tetraketopyrene 108.3 and {[Ru(bpy)2(5,6-diamino-1,10phenanthroline)](PF6)22H2O} with a 64% yield. C30.1
formed dimers in solution maintained only by stacking
of the bridging ligand, stable enough to be observed not only by
1
H NMR spectroscopy but also by electrospray mass
spectrometry at low accelerating cone voltage. Subsequent
work by Gourdon, Chiorboli, and co-workers indicated a
relatively weak interaction between the RuII units and the
bridging ligand.570 A related ligand, C30.2a, reported in 2014
by Ruan, Li, Chang, and co-workers, exhibited selective oon
uorescence response to Cd2+ over other metal ions, and the
detection limit was as low as 0.02 M.608 The Cd2+ sensing of
C30.2a had a high water tolerance and could be carried out in
aqueous media with the water content of up to 70%. C30.2a
was also successfully applied to the in vivo imaging of
intracellular Cd2+ in living HeLa cells, showing low cytotoxicity
and cell membrane permeability in these experiments. A
dierently substituted analogue, C30.2b, was employed by
Ruan et al. as a Hg2+ chemosensor.573
Chart 30. Pyrazacene-Based Ligands
Acetylene substitution was explored as a means of tuning the

electronic and geometrical properties of pyrazacene oligomers
by Mateo-Alonso and co-workers.609 Hexacenes C31.1ac,
C31.2, C31.3a (Chart 31) and octacenes C31.6ac were
originally synthesized by direct condensations of prefunctionalized amines and ketones. It was subsequently found that
increasing the bulk of silyl substituents in the C31.3ac series
of compounds results in twisting of the aromatic backbone,
with a 24 quinoxalinepyrene twist angle observed for
C31.3c.610 The twist was found to aect the energy ordering
of LUMO and LUMO+1 levels. Ethynyl-substituted C31.4 and
C31.5, bearing electron-withdrawing terminal CN and NO2
groups, exhibited signicant lowering of the LUMO levels, with
an ELUMO value of 4.3 eV reported for C31.5.563 A similar
synthetic approach was used by Miao and co-workers for the
preparation of pyrene-fused tetraazaheptacene (C31.8) and
tetraazaoctacene (C31.7).579 An additional advantage of using
bulky silyl groups was the enhanced solubility of the above
materials in organic solvents. An alternative strategy of making
CG
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Chart 31. Ethynyl- and Alkyl-Substituted Pyrazacenes563,609,610
Chart 32. Pyrene-[e]Fused Azaacenes with Terminally Condensed 5-Membered Rings
containing C32.1a and PCBM showed an absorption red shift

of 26 nm. NIR electrochromism was observed for C32.1a, with
absorption being turned on at 1034 nm when electrochemically
switched (at 1000 mV) from its neutral state to a radical cation
state. C32.1ab emit above 1000 nm with quantum yields
below 2% and large Stokes shifts (256318 nm). Variabletemperature photoluminescence data obtained for the C32.1a
lm suggested that the nonradiative decay was diminished by
restriction of bond rotations, leading to luminescence enhancement. A related class of molecules, C32.2ad, containing
soluble pyrazacenes is the use of linear alkyl chains on the

pyrene core, as demonstrated by Mateo-Alonso and coworkers.611 In the hexaoctyl system C31.9, the four alkyl
chains were installed by quadruple Sonogashira coupling
followed by catalytic hydrogenation. The product displayed a
solubility of more than 20 mg/mL in chloroform.
In 2009, Wang and co-workers prepared a series of lmforming, low-bandgap chromophores C32.1ab (Chart 32).612
Terminal fusion of 1,2,5-thiadiazole rings to the hexacene core
resulted in bandgaps of 1.271.22 eV. Two-component lms
CH
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Scheme 112. Synthetic Routes to Pyrene-Fused Azaacenesa
Reagents and conditions: (a)616 benzyltrimethylammonium tribromide, DCM, MeOH, 12 h, rt; (b) NaIO4, H2O, RuCl3xH2O, DCM, dioxane, Ar
atm, 18 h, rt; (c) 1,2-diaminobenzene, AcOH, Ar atm, 4 h, reux; (d) boronic acid, 2 M K2CO3, Pd(PPh3)4, toluene, EtOH, Ar atm, 24 h, 90 C.
Chart 33. Pyrene-[e]Fused Acene Derivatives588,599,617
spins were respectively ferromagnetically and antiferromagnetically coupled, indicating a change in the exchange coupling
pathways. The more extended biradical C32.5 was used to
show that the parameter-free extraction of distances and relative
orientations of spin centers in nucleic acids can be achieved by
orientation-selective PELDOR experiments using common Xband frequencies.615
In the majority of reported pyrazacene systems, the pyrene
cores are either unsubstituted or bear identical substituents at
positions 2 and 7. Unsymmetrical substitution patterns were
developed in 2013 by Hu, Yamato, and co-workers, starting
from 1,3-dibromo-7-(tert-butyl)pyrene 112.2, which was found
terminal cyclic imides as acceptor functionalities, was reported

in 2012 by Chi et al.613 These systems displayed LUMO
energies in the range from 3.4 to 3.5 eV, with bandgaps of
ca. 2.8 eV.
As part of their work on spin labels for use in pulsed
electronelectron double resonance (PELDOR), Prisner,
Sigurdsson, Schiemann, et al. prepared isomeric biradicals
C32.3 and C32.4, which were characterized by favorable
rigidity, while providing the necessary dierence in the
intramolecular spinspin distances.614 The two species were
obtained by oxidation of the respective diamines assembled in
diaminediketone condensations. In C32.3 and C32.4, the two
CI
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Chart 34. Heteroacenes618620
to form in good yield in direct bromination of 112.1 with

benzyltrimethylammonium tribromide (Scheme 112).616 The
bromines then served as attachment points for introducing aryl
substituents via Suzuki coupling. These arylations could be
performed directly on 112.2 or on the preassembled hexacene
112.4. In either route, the oxidation to the tetraketone was
achieved in moderate yields using the NaIO4/RuCl3 reagent.
Stepwise dionediamine condensations were used in 2008
by Wang and co-workers in their synthesis of extended acenetype molecular ribbons.599 The shortest systems, hexacenes
C27.1ac (Chart 27), served as the prototypes for the longer
ribbons C33.14, containing up to 6 pyrazine units, and up to
16 rectilinearly arranged fused benzene rings (Chart 33). The
energy gaps of these molecules, estimated from the absorption
onsets, decreased with the increase in molecular length,
covering the range from 2.66 to 2.18 eV in the C27.1c,
C33.1b4b series. Similarly, the onset of the rst reduction
wave was shifted from 1.16 to 0.62 V (vs Ag/AgCl),
corresponding to the LUMO energy levels of 3.24 and 3.78
eV, respectively, indicating a length dependence of the potential
n-type semiconductor properties. With the increasing molecular
length, the ribbons tend to aggregate in solution more readily,
as evidenced by 1H NMR and UVvis absorption spectra. It
was however found that the introduction of t-butyl substituents
noticeably suppressed aggregation. A liquid-crystalline derivative C33.1c, reported subsequently by Cheng and co-workers,
revealed a three-dimensionally ordered columnar phase stable
over a temperature range of ca. 145215 C.588 Dodecacene
derivatives C33.5ab containing a single pyrene subunit and
12 nitrogen atoms were reported in 2012 by Chan, Chi, et al.617
These compounds were obtained by a condensation reaction
between tetraketopyrene and appropriately substituted
5a,6,11,11a-tetrahydroquinoxalino[2,3-b]quinoxaline-2,3-diamines. These expanded pyrazinacenes showed good solubility
in chlorinated solvents, but their strong tendency to aggregate
in solution led to extreme broadening of their NMR spectra.
The latter eect could however be suppressed by protonation.
A linear pyrazacene C34.1 with terminal pyrene units was
reported in 2010 by MateoAlonso, Paolucci, Prato, et al.
(Chart 34).618 This poorly soluble, unsubstituted system,
prepared alongside the tetraazaoctacene C31.6d, showed strong
aggregation in solution, which was however minimized by
dissolution in acetic acid. C34.1 displayed an oxidation wave
and three reduction waves, which was considered unusual for
an azaacene containing fewer than 11 linearly fused rings. A
phototransistor device based on a C34.1 single crystal
demonstrated good performance in signal amplication under
the photoconductive eect and could be functionalized as
photocontrolled switches.619 Higher analogues of C34.1,
nonacenes C34.2 and C34.3, were prepared in 2014 by Hu,
Zhang, et al.620 UVvis spectra and electrochemical data
indicated that compound C34.2 possessed a smaller bandgap
than that of C34.3, indicating that the conjugation was
disrupted by the inclusion of oxygen atoms.
A condensation of tetraketone 111.1a with the triangular
hexamine 113.1 was reported by Jiang and co-workers to yield
a chemically stable, electronically conjugated organic framework 113.2 (Scheme 113).621 In 113.2, the -conjugated twodimensional sheets are slip-stacked, forming nanochannels with
a diameter of 1 nm, which were shown to incorporate C60
molecules and enable H2 adsorption. 113.2 demonstrated a
very high hole mobility of 4.2 cm2 V1 s1, and was shown to be
a useful material for high ono ratio photoswitches and

photovoltaic cells.
In 2014, Mastalerz and co-workers developed a family of extended D3h-symmetric triptycene derivatives 114.3ae,
which were obtained by condensing the triptycene hexaketone
114.2 with appropriate diamines (Scheme 114).622 114.3ae
are uorescent and exhibit high internal molecular free volumes
(IMFVs). They were shown to form micropores in the solid
state, with high surface areas and narrow pore-size distribution.
In subsequent work, the Mastalerz group reported the linear
bis-triptycene system 114.4, which combined good solubility
with a high tendency to crystallize.623 In the solid state, 114.4
showed noticeable bending of the aromatic core, which was
rationalized in terms of dispersive interactions. Despite the
presence of the undecacene substructure, 114.4 is a stable
compound, although it undergoes a slow photooxidation to the
quinone 114.5 under ambient conditions.
4.7. Other [e]Fused Pyrenoids
4.7.1. Pyrrole- and Indole-Containing Systems. Two

examples of indole-fused pyrenoquinones 115.12 were
described by Vollmann et al. in their extensive account of
pyrene chemistry (Scheme 115).541 These systems were
obtained by cyclization of the respective p-tolylaminosubstituted pyrenoquinones using either sulfuric acid, AlCl3 in
pyridine, or the AlCl3NaCl melt. Indole-fused pyrenes
115.46 were reported in 2015 by Lee and Park.624 115.4
was synthesized by Cadogan cyclization of 115.3 and further
functionalized using CC and CN coupling reactions. 115.6
was used as a nondoped emitting layer in OLED devices,
yielding a turn-on voltage of 3.1 V and current eciency of 3.99
cd/A.
Pyreno[4,5-c]pyrrole 116.5 (more correctly, phenanthro[4,5efg]isoindole) and its ethyl ester 116.4 were synthesized by
Lash et al. using the ZardBarton reaction followed by ester
cleavage (Scheme 116).625 4-Nitropyrene 116.3, required as
the starting material, cannot be obtained by direct nitration and
was prepared via the hexahydro intermediate 116.1. The
pyrenopyrroles are key intermediates for the synthesis of
[b]fused pyrenoporphyrins, which are discussed in section 7.1
CJ
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Scheme 113. A Pyrazacene-Based Covalent Organic Frameworka
Reagents and conditions: (a)621 (1) 113.1 chloride, ethylene glycol, 3 M AcOH, ultrasound, 15 min, 25 C, (2) in autoclave, 3 days, 120 C.
Scheme 114. Synthesis of PyrazaceneTriptycene Hybridsa
Reagents and conditions: (a)622 KOAc, chloroform, EtOH, glacial AcOH, Ar atm, 16 h, 85 C; (b) KOAc, DCM, glacial AcOH, 15 h, 70 C; (c)623
CDCl3, spontaneous photooxidation under ambient lighting.
a
monoimidazoles were synthesized in 1971 by Sakaino and

shown to form charge-transfer complexes with chloranil.627 The
interest in such derivatives was revived recently, and functionalized pyreno[4,5-d]imidazoles are now being explored as dyes
for dye-sensitized solar cells628,629 (e.g., C35.1628), ligands 630634 (e.g., C35.2, 630 and C35.3 631 ), uorophores,635637 and mechanochromic materials (e.g., C35.4636)
(Chart 35). A NiII-catalyzed variant of the Debus reaction was
reported in 2014 by Maiti and co-workers.638
The bisimidazole-fused pyrene 117.1, prepared from the
tetraone 111.1a via a double Debus annulation (Scheme 117),
was used by Lu and co-workers as a dicarboxylate building
block for the synthesis of a CuII-based MOF material.639 The
resulting structure was highly porous, consisting of noninterpenetrating square grids, with a size of 25.5 25.5 2, and
was additionally stabilized by layer-to-layer NHN interactions
forming a unique hydrogen-bonded network with a 6482-nbo
along with structurally related pyrenophthalocyanines (Chart

56 and Scheme 193).
Highly photostable, anthracene-fused BODIPY dyes 116.7
8 were developed in 2011 by Wu et al.626 The synthesis
involved FeCl3-promoted oxidative coupling of the nonfused
precursor 116.6, which produced a mixture of monomeric and
dimeric fused BODIPY products. Both dyes showed similarly
small optical bandgaps, indicating a relatively weak interaction
of the subunits in the dimer, with absorptions extending up to
ca. 950 nm, and weak NIR emission above 900 nm.
4.7.2. Imidazole-Containing Systems. In analogy to
quinoxaline condensation, which is the synthetic basis of
pyrazacene chemistry, the DebusRadziszewski reaction
provides a straightforward access to functionalized pyreno[4,5-d]imidazoles and 4,10-dihydropyreno[4,5-d:9,10-d]diimidazoles, which are prepared, respectively, from pyrene4,5-diones and pyrene-4,5,9,10-tetraones. Apparently, the rst
CK
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Scheme 115. Indole-Fused Pyrene Derivativesa
Chart 35. Pyreno[4,5-d]imidazoles
Reagents and conditions:624 (a) triethyl phosphite, o-DCB, reux, 24

h; (b) Pd(OAc)2, 2 M, K2CO3, THF, reux, 6 h; (c) CuI, 18-crown-6,
K2CO3, DMA, reux, 24 h.
depend on the relative congurations of N-substituents. In

2014, Peris and co-workers prepared a series of pyrene-based
bisazolium salts starting from 4,5,9,10-tetrabromo-2,7-di-tertbutylpyrene 117.3.643 Subsequently, multiple Buchwald
Hartwig aminations were employed to convert 117.3 into
tetraamines 117.4ab. Interestingly, the bisannulations performed with trialkyl orthoformates yielded the imidazolium
systems 117.5ac, which unexpectedly contained alkyl groups
introduced by the orthoformate. This result allowed the
preparation of derivatives with linear alkyl groups, which
could not be prepared otherwise, because of the restriction of
the BuchwaldHartwig coupling to amines with no hydrogens. A still dierent behavior was observed, when tri-nbutyl orthoformate was used. This reaction yielded the
dealkylated product 117.8, which was converted into 117.5d
in two steps. 117.5ad were all uorescent, with emissions in
the range of 370420 nm and quantum yields of 0.290.41.
Several bis-Rh and bis-Ir complexes were subsequently
prepared, such as 117.67 in which 117.5ac acted as a
bridging bis(N-heterocyclic carbene) ligand. Electrochemical
data indicated that, despite the conjugated character of the
bridging ligand, those dimetallic complexes consisted of two
essentially decoupled metal fragments.
In 2014, Baitalik et al. employed the 4,10-dihydropyreno[4,5d:9,10-d]diimidazole motif for the construction of a terpyridine-containing ligand C36.1 (Chart 36).644 Light-harvesting
bimetallic RuII complexes C36.2ab and C36.3, containing a
C36.1 bridge, exhibited room-temperature emissions in the
range of 657703 nm with lifetimes between 5.8 and 67.0 ns.
Detailed temperature-dependent emission spectroscopic studies
showed that in all three cases, decreasing the temperature led to
an increase of emission intensity, quantum yield, and lifetime.
The electronic communication between the two ruthenium
centers was evidenced by the presence of intervalence charge
transfer transition (IVCT) bands in the NIR region of the
spectrum when the mixed-valence species (RuII/RuIII) were
electrochemically generated. An analysis of these IVCT bands
indicated that couplings in these complexes were considerable,
despite the large metalmetal distances (30 ).
4.7.3. Other Nitrogen-Containing Systems. A stable,
twisted heteroacene 118.3, containing terminal pyrene and
pyridinone moieties, was reported in 2012 by Wudl, Zhang, and
Scheme 116. Pyreno[4,5-c]pyrroles
a
Reagents and conditions:625 (a) Na, n-pentanol, reux; (b)
Cu(NO3)2, Ac2O, rt, 8 h; (c) DDQ, toluene, reux, overnight; (d)
phosphazene base 172.2, ethyl isocyanoacetate, THF, rt, overnight;
(e) KOH, ethylene glycol, hydrazine, reux, 1 h; (f)626 FeCl3, MeNO2.
topology. Related derivatives 117.2ab, exhibiting deep-blue

uorescence and high thermal stability, were subsequently
reported by Lu et al.640 Subsequent work from the groups of
Lu641 and Huang642 showed that the emission properties
CL
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Scheme 117. Synthetic Routes to PyreneImidazole Hybridsa
Reagents and conditions: (a)639 4-carboxybenzaldehyde, NH4OAc, glacial acetic acid, 2 h, reux; (b)640 aniline, NH4OAc, benzaldehyde for 117.2a
or 9H-carbazole-9-carbaldehyde for 117.2b, 2 h, reux; (c)643 NaOtBu, Pd(OAc)2, 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride, tertbutylamine for 117.4a or tert-amylamine for 117.4b, toluene, overnight, reux; (d) HBF4OEt2, trimethyl orthoformate for 117.5a or triethyl
orthoformate for 117.5b or tripropyl orthoformate for 117.5c, 16 h, reux for 117.5a,b or 24 h, 150 C for 117.5c; (e) [IrCl(cod)]2, KOtBu, THF,
overnight, rt; (f) CO gas, DCM, 20 min, 0 C; (g) tributyl orthoformate, HBF4OEt2, 24 h, 150 C; (h) (1) NaOH, dimethylsulfoxide, 2 h, rt, (2) Nbutyl bromide, 30 min, rt, (3) overnight, 37 C, (4) N-butyl iodide, 24 h, 100 C; (i) [Et3O][BF4], DCM, 30 min, rt.
Scheme 118. Synthetic Route to a Twisted Heteroacenea
Chart 36. Bimetallic RuII Complexes Containing a

Pyrenodiimidazole Bridge644
a
Reagents and conditions: (a)645 isoamyl nitrite, dichloroethane, 2 h,
reux; (b) vacuum, 4 h, 220 C; (c) tetrahydronaphthalene, 4 h, 220
C; (d)646 isoamyl nitrite, dichloroethane, reux, overnight.
Compound 118.3 is green in dichloromethane solutions, with

an optical band gap of 1.86 eV, comparable to that of hexacene.
Upon addition of a strong Lewis acid, such as anhydrous ZnCl2,
a considerable blue shift was observed in the spectrum of 118.3,
which was assumed to result from an interaction with the
carbonyl oxygen. Analogous reactions performed on 118.1
co-workers (Scheme 118).645 Its synthesis involved a [4+2]

cycloaddition between the aryne dienophile generated from
118.1 and a mesoionic pyrimidine as the diene. The
intermediate adduct 118.2 was subjected to thermal cycloreversion, yielding the lactam 118.3 in excellent yields.
CM
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Scheme 119. Pyrenofuransa
Reagents and conditions: (a)647 (1) furan, 1.6 M n-BuLi, 2 h, 70 C, (2) overnight, rt; (b) dipyridyltetrazine, chloroform, 18.5 h, reux; (c) (1)
dipyridyltetrazine, chloroform, overnight, rt, (2) N,N-1,5-bis(maleimido)propane or N,N-1,5-bis(maleimido)pentane, 1 h, rt.
a
Scheme 120. Synthetic Pathways to [e]Fused Furanopyrenoidsa
a
Reagents and conditions: (a)652 (1) cyclic ketone, 5 min, rt, (2) FeCl3, 12 h, rt; (b)651 CF3SO3H, m-cresol, N2 atm, 24 h, 180 C; (c)652 allyl
bromide, In powder, NaI, DMF, 4 h, rt; (d) (1) NaBH4, MeOH, 10 min, 0 C, (2) 8 h, rt; (e) I2, THF, 12 h, rt; (f) DBU, DMF, 4 h, 50 C; (g)653
(1) benzylphosphonium chloride or p-bromophenylmethylphosphonium bromide, potassium t-butoxide, dimethyl sulfoxide, 30 min, rt, (2)
dihydrofuran, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, toluene, 4 h, 70 C; (h)648 alkyl vinyl ketone, TiCl4, DCM, rt, 3 h; (i)650 4methoxyphenol, TFA, o-DCB, reux.
The 1H NMR spectrum of 119.4a indicated that the short

aliphatic tether was conformationally restricted within the
cyclophane.
Dione 108.1 is a convenient starting material for the
synthesis of [e]fused furan derivatives (Scheme 120). By
subjecting 108.1 to a tandem condensation, on the basis of the
BaylisHillman reaction, Basavaiah et al. obtained a range of
formyl substituted furans 120.11,648 as well as a range of
alicyclic analogues such as 120.13.649 Electrophilic cyclization
of 108.1 with a variety of phenols, explored in 2015 by Xiao,
Ba, et al.,650 was shown to produce fused furans, such as
120.12, 120.14, and 120.15 in moderate yields. These furans
were strongly uorescent and exhibited self-assembly into
nanostructures, tunable by reprecipitation conditions.
using diaryl-1,2,4,5-tetrazines as the diene reagent produced the

diazatwistpentacenes 118.4ac.646
4.7.4. Oxygen-Containing Systems. In 2009, Dibble et
al. reported the synthesis of pyreno[4,5-c:9,10-c]difuran 119.3
and its transformation into pyrenophanes 119.4 (Scheme
119).647 119.3 was obtained by means of a cycloaddition
cycloreversion procedure, developed in 1988 by Moursounidis
and Wege for the synthesis of the monofuran analogue
119.5.549 In the rst step, arynes generated sequentially from
119.1 were subjected to a double furan cycloaddition. The
resulting bisepoxide intermediate 119.2, which formed as a
mixture of syn and anti isomers, was reacted with
dipyridyltetrazine to give 119.3. This difuran was reacted
with tethered bis(maleimide) dienophiles, yielding pyrenophanes 119.4ab, which were characterized in the solid state.
CN
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An acid-catalyzed condensation of 108.1 with m-cresol was

reported in 2011 by Zhang and co-workers to yield the
benzofuran system 120.1c in moderate yield.651 Nanowirebased lms, obtained by reprecipitation of 120.1c in THF/
water mixtures, showed enhanced performance in organic lightemitting diodes in comparison with thin lms of 120.1c
deposited by direct drop-coating of the THF solution. An
alternative route to benzofuran-fused systems 120.1ad was
developed by Rao and Vijjapu, who condensed 108.1 with
cyclohexanone and its derivatives under oxidative conditions.652
Absorption and emission spectroscopic studies revealed the
bathochromic eect of benzofuran annulation on the photophysical properties of the pyrene chromophore, and an
associated increase of uorescence quantum yields. In the
same work, 10-methylpyreno[4,5-b]furan 120.5 was prepared
in four steps starting from 108.1. Indium metal-mediated
allylation of 108.1 rst yielded the ketoalcohol 120.2, which
was stereoselectively reduced at the carbonyl group, furnishing
the trans-diol 120.3. The iodine-mediated cyclizationelimination of 120.3 produced the dihydrofuran derivative 120.4,
which underwent nal dehydroiodination to 120.5. In 2014,
Kawase et al. reported the synthesis of highly uorescent
pyreno[4,5-b]furans 120.6ab and the related isomeric
pyrenodifurans 120.7 and 120.8. In these systems, the furan
ring closure was achieved by reacting the 1,2 dione fragment
with 2 equiv of an appropriate benzylidenephosphorane.653 An
alternative, more complex approach to [e]furano-fused
pyrenoids was described in 1985 by Royer et al.654 Instead of
108.1, they used as the starting material the aldehyde 120.9,
which is available from pyrene in six steps. By condensing the
latter aldehyde with bromonitromethane or ethyl bromoacetate,
substituted furans 120.10ab could be obtained in good yields.
Pyreno[4,5-b]oxepine 121.3 was obtained by Boyd and coworkers as one of the products of base-induced eliminations
performed on both racemic and enantiopure bromoacetates
121.1 (Scheme 121).655 121.3 formed alongside the isomeric
epoxide 121.2, which was produced as a racemic mixture
regardless of the enantiopurity of the starting 121.1.
Scheme 122. Benzo[b]benzo[10,11]chryseno[6,5d]thiophenea
Reagents and conditions: (a)556 (1) phenyllithium, (2) 2,2,2,2tetraethoxydiethyldisulde; (b)556 PPA, chlorobenzene, reux; (c)656
HBr/H2O/AcOH, pressure tube, 188 C; (d)656 AlCl3, benzene, 10
min, reux.
this approach was described in 2011 by Mullen and co-workers,

who prepared the substituted benzo[8,9]triphenyleno[1,2b:4,3-b]dithiophene 123.3 using a sequence of Stille coupling
and photochemical dehydrocyclization (Scheme 123).657 The
latter ring-closure turned out to be crucial for utilization in
solution-processed OFET devices, and 123.3 showed an
exceptional hole mobility for a perylene-based system. Related
work from Duan, Nishioka, et al.658,659 and from the Mullen
group660 described the preparation of the tetrathiophene
system 123.5ac. These molecules were similarly obtained,
by using either photochemical or chemical oxidation in the
ring-forming step (123.5a could not be obtained via chemical
oxidation). In the solid state, 123.5b has a saddle-shaped conjugated 1D supramolecular structure, which favors highly
ordered self-assembly by interactions, as evidenced by its
concentration-dependent 1H NMR spectra in solution. 123.5b
showed a relatively large band gap (2.86 eV), low EHOMO level
(5.64 eV), indicative of its potential use as a stable holetransporting material.
An approach to the synthesis of pyreno[4,5-c][1,2,5]thiadiazole 124.6 and its oxides was developed in 2010 by
Sutherland, Baumgartner, and co-workers (Scheme 124).661
The initial ring closure was performed on the bis-TMS
derivative 124.1, yielding the S-oxide 124.3, which was reduced
to 124.6 as well as oxidized to the S-dioxide 124.4. An
alternative pathway to 124.6 was reported in 2013 by Xiao,
Jiang, et al.662 Their synthesis involved direct condensation of
pyrene-4,5-diamine 124.5 with thionyl chloride. Additionally,
pyreno[4,5-c][1,2,5]selenadiazole 124.7 was obtained from the
same diamine in a reaction with SeO2. A very dierent synthesis
of 124.6, based on oxidative cyclization of the cyclophane
precursor 124.8, was reported in 1991 by Mataka and coworkers.663 Increasing the number of S-bound oxygens in the
series 124.6, 124.3, 124.4 resulted in a gradual shift of the rst
reduction potential (2.08, 0.88, 0.66 V vs Fc/Fc+),
providing access to building blocks for n-type semiconducting
polymers.661 Upon reprecipitation from THF, 124.6 produced
nanowires 160400 nm in diameter, whereas 124.7 yielded
quadrangle-type nanostructures with the morphology dependent on the precipitation conditions.662
Scheme 121. Synthesis of Pyreno[4,5-b]oxepina
(a)655 NaOCH3, THF, 2 h, 0 C, 121.3 was the major product; (b)

NaOCD3, THF-d8, NMR control, 121.2 (70%), 121.3 (30%).
4.7.5. Sulfur-Containing Systems. In 1981, Castle et al.

reported a synthesis of pyreno[4,5-b]thiophene 122.3.556 Their
low-yielding procedure involved the initial formation of a
thioether 122.2, which was subjected to acid-catalyzed
cyclization under fairly harsh conditions. Benzo[b]benzo[10,11]chryseno[6,5-d]thiophene 122.6 was prepared in 1966
by Henson and Vingiello (Scheme 122).656 This ring system
was obtained by oxidative cyclization of the benzo[b]thiophene
precursor 122.2 under Scholl conditions. 122.5 and related
derivatives were obtainable in a highly ecient, acid-catalyzed
cyclization of benzyl phenyl ketones, such as 122.4.
A more recent approach to thiophene-fused pyrenoids relies
on oxidative coupling of 2-thienyl substituents. An example of
CO
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Scheme 123. Thiophene-Fused Pyrenesa
Reagents and conditions: (a)657 2-(tributylstannyl)thiophene, Pd(PPh3)4, toluene, overnight, reux; (b) I2, h at 300 nm, toluene, overnight; (c)658
Pd(PPh3)4, DMF, 100 C; (d)660 Pd(PPh3)4, toluene, Ar atm, 110 C, 716 h; (e) I2, h at 300 nm, toluene, Ar atm, overnight, rt; (f)658,659 FeCl3,
CH3NO2, DCM, 0 C, 15 min; (g)660 FeCl3, CH3NO2, DCM, Ar atm, rt, 30 min.
Scheme 124. Pyreno[4,5-c][1,2,5]thiadiazole and Related

Systemsa
Chart 37. Classication of Phenalenoids Used in This

Sectiona

indicated.
a
to phenalene results in the pyrene substructure). Interestingly,

among the systems presented in this section, the choice of
heteroatoms is virtually limited to nitrogen, oxygen, and sulfur.
An isolated example of a boron-containing phenalenoid (39.7,
Scheme 39) is shown in section 3.1.
Large phenalenoid structures with ortho-fused heterocycles
have been explored to a limited extent. A range of phenalene-1one derivatives have nevertheless been reported, including
heterofused benzo[de]anthracen-3-ones C38.1665 and C38.2666
(Chart 38), and benzanthrones (benzo[de]anthracen-7-ones),
containing pyridine (C38.34,667 C38.5668), pyridinone
(C38.67669), imidazole (C38.8,670 C38.9,671 C38.11
12672), oxazole (C38.10673), and indole (C38.13478) moieties.
Fluorescent anthra[9,1-gh]quinoline dyes C38.5, obtained in a
Skraup synthesis, were shown to have a very good orientation
parameter in nematic liquid crystal (SA = 0.640.67), indicating
a high potential for applications in display technology.668
Reagents and conditions: (a)661 SOCl2, toluene; (b)661 m-CPBA;

(c)662 SnCl2H2O, HCl (conc.), anhydrous EtOH, 70 C, 5 h; (d)661
PPh3, CCl4; (e)662 SOCl2, TEA, DCM, reux, 4 h; (f)662 SeO2, EtOH;
(g)663 NBS, benzoyl peroxide, CCl4.
5. PHENALENOIDS
The tricyclic phenalene ring system is the smallest graphene
substructure containing a peri-fusion point. The phenalene
framework contains an odd number of carbon atoms and has to
be further modied to yield neutral, fully conjugated molecules
with a closed-shell character. Simultaneously, this structural
feature provides for the stability of phenalene-based radicals,
which have been intensely explored.664 In line with the scope of
this Review, this section is mostly restricted to phenalenoids
containing at least 20 atoms in the ring system, a number that
corresponds to at least two additional ortho-fused rings. As in
previous sections, we exclude from our discussion derivatives of
naphthalene anhydrides, imides, and their simple condensation
products. Heteraphenalenes containing an increasing number
of heteroatoms are discussed in sections 5.1, 5.2, and 5.3 (Chart
37). Phenalenes containing peri-fused 5- and 7-memebred rings
are presented in section 5.4 (peri-fusion of a six-membered ring
5.1. Monoheteraphenalenes
5.1.1. Heterahelicenes. In the course of their investigations of heteratriangulenes (section 4.1) and following
earlier work by Hellwinkel and Melan,357 Venkataraman et al.
reported the synthesis of several quinolino[3,2,1-de]acridine5,9-diones358 (Scheme 125). The prototypical systems,
containing ve fused rings, were obtained by double intramolecular acylation of appropriately substituted triarylamines,358 exemplied by the conversion of 125.1 to
125.2.674 125.2 can be viewed as a [4]helicene derivative,
and the work was extended to include higher helicenes, 125.3
and 125.4.674 Similar to carbocyclic helicenes, these systems
CP
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Chart 38. Hetero-Fused Phenalene-1-one Derivatives
Scheme 125. Triarylamine-Derived Heterahelicenesa
5.1.2. 9a-Azaphenalene Ylides. The chemistry of 9aazaphenalene ylides was independently disclosed in 2014 by the
group of Mullen680 and by Ito, Tokimaru, and Nozaki.681 Both
groups presented a similar synthetic approach, in which a
functionalized m-terphenyl 126.1 was cyclized and oxidized to
the phenanthridinium salt 126.2 in either one680 or two681
steps. 126.2 could be easily deprotonated with triethylamine,
but the resulting ylide 126.3 was too unstable to be isolated.
126.3 is ESR-silent and yielded a complex but suciently
resolved 1H NMR spectrum at 60 C,680 in line with the
closed-shell structure predicted for the ylide using DFT
calculations.681 The extended conjugation in 126.3 is
however evident from the electronic spectrum, which shows a
broad band at 580 nm.
126.3 was shown to be a reactive dipole in the [3+2]
cycloaddition, yielding a range of adducts, such as 126.4a680 or
126.9,681 and a dimerization product, 126.8.680,681 Acetylene
adducts were occasionally observed to undergo spontaneous
dehydrogenation (as in 126.5b681), or could be dehydrogenated with DDQ (126.5a680 and C42.14, Chart 42, section
5.4682). A phenyl-substituted salt 126.7 was obtained from
126.3, by using Grignard addition followed by hydride
abstraction, and was further deprotonated to yield the
corresponding ylide 126.6.680
The double ylide 126.12, the higher homologue of 126.3,
was synthesized as a model of an N-doped zigzag graphene
nanoribbon.680 The synthesis of the precursor salt 126.11
followed the strategy established for 126.2 and 126.7, with a
separate hydride removal step. 126.12 could only be generated
in solution, revealing an extended optical absorption with
maxima at 685 and 751 nm. DFT calculations performed for
126.3, 126.12, and their predicted higher homologues
indicated the zwitterionic nature of the azodimethine moieties
and the retention of Clar sextets in the ribbon framework. A
singlet ground state was predicted for all systems up to the
tetramer, with a gradual reduction in the singlettriplet gap
with increasing ribbon length.
5.1.3. Ceramidonines. Naphtho[3,2,1-kl]acridin-9-ones,
known as ceramidonines or ceramidones, are obtained by
dehydration of 1-arylaminoanthraquinones under acidic conditions.683 Syntheses of hydroxy-substituted ceramidonines
such as 127.2 were reported in 1945 by Cook and
Waddington146 (Scheme 127). In these reactions, the
a
Reagents and conditions: (a)674 Cu or CuI, K2CO3, Ph2O or (nBu)2O, 150190 C, 25 days; (b)674 (1) NaOH, H2O/EtOH (1:1),
reux for 13 days, then HCl, (2) (COCl)2, CH2Cl2, reux, 0.5 h,
then SnCl4, reux 23 h.
show helically chiral, nonplanar conformations in the solid

state, but their racemization barriers were not determined.
125.24 showed strong uorescence in the visible range (460
490 nm). Subsequent work led to camphanate-substituted
enantiopure helicenes 125.56, which produced circularly
polarized luminescence with dissymmetry factors of |
0.001|.675 Acetylene linked homochiral bishelicene 125.7 was
obtained by subjecting a Br-substituted helicene to double Stille
coupling.676 125.57 were explored using uorescence
excitation circular dichroism on a single-molecule level.677679
CQ
Chemical Reviews
Review
Scheme 126. 9a-Azaphenalene Ylidesa
a
Reagents and conditions: (a)680 HCl in dioxane (4 M), microwave, O2; (b)680 TEA (not isolated); (c) R = COOMe:680 DMAD, TEA, DCM, 25
C; R = Ph:681 diphenylacetylene, toluene, 100 C; (d)682 DDQ, toluene, 25 C; (e)680 PhMgBr, THF, 0 C; (f)680 [Ph3C][BF4], toluene, MeCN,
90 C; (g)680 DMSO, NBu3, 190 C; (h)681 C60, TEA, o-dichlorobenzene, 40 C, 18 h.
extending up to 650 nm, and exhibited pinkish-violet

uorescence with maximum emission at 665 nm.688 Bock and
co-workers extended the classical ceramidonine synthesis to
obtain mono- and bis-ceramidone derivatives 127.1517.147
127.16 and 127.17 showed continuous absorption up to ca.
500 nm.
5.1.4. Dibenzo[c,mn]acridin-8-ones. The parent system
128.2 (benzo-semiavanthrene, Scheme 128), isomeric with
ceramidone, was apparently rst obtained by Koelsch in
1936,720 although related structures were postulated in earlier
work on avanthrone (Scheme 83, section 4.2) by Scholl and
co-workers.721,722 128.2 and its derivatives were obtained by
cyclization of appropriate phenanthridine,720 anthraquinone,163,723 and imine724 precursors and by extrusion of the
thiazepine derivative 128.1.164 Larger fused derivatives 128.3725
and 128.4726 were reported by Wick.
5.1.5. Monooxa- and Monothiaphenalenoids. The
majority of pyran- and thiopyran-containing phenalenoids,
are, respectively, derivatives of benzo[kl]xanthene and benzo[kl]thioxanthene. In particular, ceroxene683,727 (naphtho[3,2,1kl]xanthene, C39.2a, Chart 39) and cerothiene derivatives
(C39.2b)728,729 were investigated in the context of dyestu
research (see ref 146 for a brief summary). These compounds
were named after von Baeyers corulen C39.1, a classical
mordant dye combining xanthene and anthraquinone motifs.730
Naphtho[1,2,3-kl]xanthenes and thioxanthenes of the general
structure C39.3 were obtained via photocyclization of the
corresponding benzylidene precursors731 or as side products in
photoadditions of aromatic ketones to arylacetylenes.732
Quinone-fused bis-xanthenes were developed by Sakla et al.
(e.g., C39.4), 733 whereas a range of phenazine-based
derivatives, such as C39.5, were reported by Ooyama, Yoshida,
cyclization was accompanied by demethylation of methoxy

substituents. 70% H2SO4 was the most typical condensation
reagent, providing access to various substitution and fusion
patterns144,146,147,478,684688 and enabling an analysis of the
condensation kinetics.689 A range of other acidic catalysts were
also used, including AlCl3 melts478,690693 and H3PO4.694,695
The reaction is generally regioselective, although the formation
of carbazole byproducts was occasionally observed.690 More
recently, ceramidonines (e.g., 127.11 and 127.13) were
obtained by direct benzyne cycloadditions to 1-aminoanthraquinone 127.9. The requisite benzyne intermediates
were generated from o-(trimethylsilyl)phenyl triate 127.10 by
Rogness and Larock696 and from 5-arylthianthrenium perchlorates (e.g., 127.12) by Kim et al.697 The reactivity of
ceramidonines in electrophilic698 and nucleophilic699 substitutions was investigated, with a range of reagents being explored,
such as amines,700710 active methylene compounds,711
arylsulnic acids,712 alkoxides,713 potassium cyanide,714 and
thiophenols.715 Functionalized ceramidonines containing striazine716 and sulfonamide717 groups were developed for use
in dyeing. Ceramidine derivatives of the general structure
146.14 were obtained by Wittig olenation of ceramidonine
127.11 by Lee et al.693
Sokolyuk and Pisulina reported a reversible photoarylotropic
rearrangement of the ceramidonine derivative 127.7, in which
the phenyl group could be induced to migrate between two
adjacent oxygen atoms by alternating irradiation with UV and
visible light.692 The use of more elaborate precursors was
explored as a means of obtaining extended fused systems, such
as 127.34718 and 127.5.719 The carbazole-linked bisceramidonine 127.6, reported by Mullen and co-workers, had
a yellowish color in solution, despite electronic absorptions
CR
Chemical Reviews
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Scheme 127. Ceramidoninesa
Reagents and conditions: (a)146 75% H2SO4, 160 C, 3 h; (b)692 visible light irradiation ( > 450 nm); (c)692 UV light irradiation ( = 300380
nm); (d)696 CsF, MeCN, 65 C, 24 h; (e)697 LDA, THF, reux; (f)693 t-BuOK, THF, 1043%.
a
Scheme 128. Dibenzo[c,mn]acridin-8-onesa
Chart 39. Monooxa- and Monothiaphenalenoids
Reagents and conditions: (a)164 diethyl phthalate, copper bronze,

reux.
et al.734,735 The Pd-catalyzed dehydrogenative cyclization

developed by the group of Zhang (cf., Scheme 100, section
4.3) was used for the construction of various fused sulfoxides,
including the dibenzo[b,mn]thioxanthene 8-oxide C39.6.527 A
smaller fused system of interest is the ferrocenyl-conjugated
pyrylium cation C39.7, obtained in 2009 by Nishihara et al., by
means of the acid-catalyzed acetylene cyclization described
above (e.g., 37.7, section 3.1).736 Unusually, this system shows

an anion-dependent valence tautomerism, the TFSI and PF6
CS
Chemical Reviews
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salts gradually switching from the FeII structure C39.7a to the

FeIII species C39.7b, as the temperature was increased. The
interaction between ferrocene and pyrylium subunits could be
switched o by nucleophile addition to the pyrylium fragment
of C39.7.737
Expanded iminocoumarins of the general structure 129.2,
and their N-protected analogues, were reported in 2015 by
Gryko, Cywinski, et al. (Scheme 129).738 These systems, which
Miserez described the synthesis of two isomeric derivatives

C40.12 in the course of their work on indigo yellow 3G.739
Related oxazole derivatives, such as C40.3, were obtained by
Kazankov et al.740,741 Gerasimenko et al. described naphthacenopyridones capable of photoinduced aryl group migration
(e.g., C40.4ab).742744 Pyrazole-fused systems C40.5 were
obtained by Shechter et al. by alkyne cycloaddition to 2diazoaceanthrenone, followed by rearrangement.745 An interesting example of an azaphenalenoid found in dyestu
chemistry2 is compound C40.6, known as C.I. Disperse Yellow
77, obtainable by condensing 1-aminoanthraquinone with
anthranilic acid. Various derivatives of C40.6 were synthesized,495,746748 including its -extended analogues such as
C40.78. The hexacyclic system C40.9 was obtained in 1984
by Katritzky and co-workers,473 using the photocyclization
approach presented in Scheme 86, section 4.2. C40.10, a 1azaphenalene derivative, was synthesized using the Graebe
Ullmann reaction by Waldmann and Hindenburg.478
A synthesis of vertically expanded imidazo[1,2-a]pyridines,
which contain the 2-azaphenalene motif, was recently reported
by Gryko and co-workers (Scheme 130).749 Using Heck-type
coupling, the unsubstituted 130.1 was converted into 3-aryl
derivatives 130.2, which were subjected to the anionradical
coupling with potassium metal to yield the fused products
130.3ae. A sequential cycloadditioncycloreversion performed with DMAD was used for further modication of the
ring system, producing fused indolizines such as 130.4.
Mullen and co-workers reported a concise method of
expanding naphthalene and perylene anhydrides via condensation with acetylanilines (for perylenoid derivatives described in
this work, see Scheme 30, section 3.1, and Scheme 65, section
3.5).136 The condensation of naphthalene monoanhydride
(NMA) with 2-acetylaniline was found to produce either of two
isomeric systems: the 4-hydroxyquinoline-fused 130.5 or the 4oxoquinoline derivative 130.6, depending on the reaction
conditions. 130.5 was the thermodynamic product of the
reaction and was available through rearrangement of the
initially forming 130.6. The latter species was further expanded
by condensation with malonodinitrile, yielding 130.7.
Scheme 129. Expanded Iminocoumarinsa
Reagents and conditions: (a)738 K2CO3, DMSO, 60 C.
display polarity-sensitive uorescence, were obtained in

moderate yields via a double annulation reaction between the
anthraquinone derivative 129.1 and substituted acetonitriles.
Interestingly, the 2 equiv of the acetonitrile reagent produced
two rings of dierent sizes, leading to products that combined
benzofuran and iminocoumarin fragments.
5.1.6. Miscellaneous Azaphenalenoids. Syntheses of
other extended azaphenalene systems were occasionally
reported in the literature (Chart 40). De Diesebach and
Chart 40. Miscellaneous Monoazaphenalenoids
5.2. Diheteraphenalenes
Out of many possible heteroatom patterns, 1,6-diheteraphenalene is encountered most frequently as the key structural motif
of pyridoacridine alkaloids and heterahelicenes. -Extended 1,4and 1,3a-diheteraphenalenes, represented mostly by quinolino[4,3,2-kl]acridines and phenoxazine derivatives, respectively, are
discussed at the end of this section. For reported examples of
1,3- and 1,9-diheteraphenalenoid systems, see refs 750753.
5.2.1. Pyridoacridines. Pyridoacridines are a family of
alkaloids isolated from marine invertebrates (tunicates, sponges,
and bryozoans) sharing the common fused motif of pyrido[2,3,4-kl]acridine (131.1).754758 The interest in these alkaloids
stems from their strong cytotoxicity and DNA binding.756 The
following discussion is restricted to reported syntheses of
pyridoacridines containing at least 5 fused rings, and showcases
key peri-annulation steps. The chemistry of the perylenecontaining alkaloid, eilatin 44.5, is discussed in section 3.1.
Ascididemin 131.2, one of the most prominent examples of
pyridoacridine alkaloids, was rst synthesized in 1989 by
Bracher, who performed self-condensation of enamine 131.6 to
close ring E in the nal step (Scheme 131).759 This approach
enabled the synthesis of related alkaloids, such as 2bromoleptoclinidone,760 neocalliactine acetate,761 and kuanoniCT
Chemical Reviews
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Scheme 130. -Expanded 2-Azaphenalenesa
Reagents and conditions: (a)749 ArBr or ArI, Pd(OAc)2, KOAc, DMA, 150 C, 5083%; (b)749 K, toluene, air, 95 C; (c)749 dimethyl
acetylenedicarboxylate, mesitylene, 150 C; (d)136 imidazole, 140160 C; (e)136 Zn(OAc)2, quinoline, 180 C; (f)136 AcOH, Ac2O, malononitrile,
reux, 31%.
a
Scheme 131. peri-Annulations in the Syntheses of Ascididemina
a
Reagents and conditions: (a)759 NH4Cl, AcOH, 1 h; (b)775 H2SO4, h, 2 h; (c)776 NaN(CHO)2, DMF, reux; (d) BBr3, DCM (78)0 C; (e)
NBS, DMF, 0 C; (f) 10 kbar, 80 C, MeCN; (g)780 NaH, DMF, MW, 95 C, 25 min; (h) O2, rt, 3 h; (i)774 CeCl37H2O, air, EtOH, reux, 9 h; (j)
25% NH3 (aq), MeOH, rt, 7 days.
amine A762,763 (131.35), as well as several synthetic

analogues.764767 A renement of the Bracher synthesis, in
which the nal ring closure was achieved by reaction with
paraformaldehyde, was reported by Copp and co-work-
ers.768771 Mechanistically related syntheses of 131.2 were

reported by the groups of Kashman772 and Echavarren.773 The
Kashman route222,772,774 is particularly ecient because it
closes two rings in a single reaction step, and enables the
CU
Chemical Reviews
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Scheme 132. peri-Annulations in the Syntheses of Pyridoacridine Alkaloidsa
a
Reagents and conditions: (a)782 (1) aq HCl/THF, 7080 C, 3 h, 86%, (2) Me2SO4, K2CO3, DMF, 23 C, 3 h, 96%; (b)789 (1) H2, Pd/C, MeOH,
91%, (2) 57% aq HI, 88%; (c)795 diphenyl ether, reux, 5 min, 74%; (d)797 chlorobenzene, acetophenone, h; (e)798 KF/Al2O3, 18-crown-6, DMSO,
120 C, 2 h; (f)802 TMPMgClLiCl (2.2 equiv).
synthesis of analogues with extended fusion, such as

benzoascididemin222 or 131.15.774 Moody et al. synthesized
ascididemin by photochemical cyclization of the iodo derivative
131.7.775 The approach of A lvarez et al.776 involved an early
closure of the E ring, performed on the acetylene intermediate
131.8, followed by the construction of ring A via a heteroDielsAlder reaction. Kristensen et al. developed an anionic
cascade reaction providing a step-ecient route to various
pentacyclic systems.777779 In a particular application of this
method, the nitrile precursor 131.12 was transformed into the
unstable deoxy intermediate 131.13, which was oxidized in situ
to ascididemin.780
In late 1980s, three synthetic approaches to amphimedine781
(132.2) were disclosed almost simultaneously by Echavarren
and Stille,782 Kubo and Nakahara,783,784 and Prager et al.785,786
In particular, Echavarrens route involved imine bond formation
on a preassembled quinone derivative 132.1 (Scheme 132). A
similar scheme was employed in the syntheses of isoascididemin by Gomez-Bengoa and Echavarren,787 meridine 132.4 by
Kubo et al. (from 132.3),788,789 sebestianine A by Delfourne et
al.,790 and related systems.791794 Meridine could alternatively
be constructed from the peri-fused precursor 132.5, which was
cyclized by brief heating in diphenyl ether.795 An alternative
peri-fusion strategy, based on intramolecular photocyclization of
aryl azides, was developed by Ciufolini et al., yielding sulfurcontaining alkaloids, such as nordercitin 132.9, kuanoniamine
D 132.10, and dercitin 132.12.796,797 Arnoamine A (132.15), a
unique pyridoacridine with a peri-condensed pyrrole ring, was
synthesized by Delfourne et al., who used intramolecular
nucleophilic substitution to simultaneously create two perifusion points.798 A range of amphimedine analogues (e.g.,
133.2ab, Scheme 133) was obtained by Wang and co-workers
by means of CuII-799 or AuI-catalyzed800 tandem bis-annulations
of N-propargylaminoquinones, such as 133.1. A Brnsted acid-
Scheme 133. Syntheses of Pyridoacridines via Tandem BisAnnulationsa
Reagents and conditions: (a)799 1 equiv of CuCl2, MeNO2, 80 C, 4

h; (b)800 Ph3PAuCl (5 mol %), AgOTf (5 mol %), TFA, rt, 1 h; (c)801
Fe2(SO4)3 (10 mol %), H2SO4/HOAc, 100 C, 2 h.
a
promoted bisannulation of quinoneethynyl precursors (e.g.,

133.3) was subsequently developed as a route to ascididemintype alkaloids.801 Another distinct cyclization strategy, relying
on a directed remote ring metalation of benzo[c][2,7]naphthyridine 132.16 with KnochelHauser base followed by
intramolecular trapping of an ester group, was employed by
Bracher et al. in the synthesis of demethyldeoxyamphimedine
132.17.802
5.2.2. Other 1,6-Diheteraphenalenoids. Outside the
eld of pyridoacridine alkaloids, the 1,6-diheteraphenalene
unit is found in several classes of heterocycles, such as the
CV
Chemical Reviews
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chromeno[2,3,4-kl]acridines 134.1803 and 134.3a804 and their

heterologues 134.3bd (Scheme 134).804 134.3ad were
The eciency of the SNAr synthesis of 135.3 is somewhat

dependent on the identity of the amine, and the competing
formation of a neutral acridine side product was observed when
benzylamine was used as the nucleophile.809 Subsequent
detailed analysis by Laursen, Lacour, et al. showed that the
135.3 cations could be resolved into enantiomers, via the
formation of diastereomeric binphat salts.810 These enantiomers were congurationally stable, but slow racemization
could be induced above 200 C. The 135.3 cations underwent
nucleophilic addition to the central carbon. The resulting
adducts (e.g., 135.10810 and 135.11811) retained the sense of
helicity present in the cation. The addition of enantiopure
sulfoxide anions yielded diastereomeric products 135.11, which
could be resolved and converted back to the diazahelicenium
cations in an unusual type of Pummerer rearrangement.811813
Diazahelicenium cations unsymmetrically substituted with two
dierent R groups reacted with hydride and organolithium
nucleophiles in a highly diastereoselective manner (dr > 49).814
Reduction of 135.3b with sodium borohydride yielded the
neutral helicene 135.14.808 The central CH bond in 135.14 was
found to be susceptible to deprotonation with strong bases, and
the resulting carbanion could be trapped as thioamide 135.15
by reaction with benzyl isothiocyanate.
The 135.3 helicenes are highly stable carbocations (pKR+
19), showing strong UVvis absorption (up to ca. 680 nm, max
> 104 M1 cm1), which is considerably red-shifted in
Scheme 134. Other 1,6-Diheteraphenalenoidsa
Reagents and conditions: (a)804 94% H2SO4, 130 C, 3 h.
prepared by acid-catalyzed cyclizationdemethylation of

xanthenone precursors 134.2ad.804 The most versatile route
to 1,6-diheteraphenalenoids was disclosed by Laursen and
Krebs in their synthesis of triheteratriangulenium salts (section
4.1).32,420,426 When tris(2,6-dimethoxyphenyl)carbenium cations 135.2 are reacted with a primary amine, the methoxy
groups are displaced in a sequence of SNAr reactions, leading,
among other products, to a range of N-substituted 1,13dimethoxyquinacridinium (diazahelicenium) cations 135.3
(Scheme 135).805
Scheme 135. Diheterahelicenesa
a
Reagents and conditions: (a)805 (1) n-BuLi, Et2O, reux, (2) (EtO)2CO, Et2O, reux, (3) aq HBF4, Et2O, rt, 85%; (b)805 PrNH2, NMP, 45 min,
110 C, 85%; (c)805 N,N-dimethylethylenediamine, N-methylpyrrolidone, 110 C, 60%; (d)805 (1) MeI, MeOH, 110 C, (2) t-BuOK, DMF, room
temperature, (3) aq HBF4, room temperature, 100%; (e)805 (1) aq HBF4, MeOH, 70 C, (2) aq Na2CO3, CH2Cl2, room temperature, 94%; (f)805
PbO2, benzene, room temperature, 99%; (g)806 (1) MeNH2 (2.5 equiv), MeCN, 0.5 h, (2) HBF4, 95%; (h)806 (1) N2H4 (2.5 equiv), MeCN, 0.5 h,
(2) HBF4, 95%; (i)806 N2H4 (aq, 25 equiv), DMF, 90 C, 814 h, darkness, 97%; (j)806 MeNH2 (25 equiv), DMF, 90 C, 1014 h, darkness, 91%;
(k)807 (1) BBr3 (2.5 equiv), DCM, (2) HBF4 (aq), (3) 100 C, neat, (4) NaBH4, EtOH, 15%; (l)807 I2, Et2O, quant.; (m)807 DMSO-d6, 120 C;
(n)808 NaBH4, EtOH, 95%; (o)808 (1) n-BuLi (2 equiv), Et2O, 40 min, 78 to 0 C, (2) BnNCS (10 equiv), 20 min, 0 C, 85%.
CW
Chemical Reviews
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comparison with the completely fused triazatriangulenium

cations. The helicene cations show NIR uorescence with
quantum yields in the 220% range and lifetimes of 112
ns.815 The interactions of 135.3 with DNA were consequently
investigated using absorption, uorescence, and circular
dichroism spectroscopies, showing that the binding is dependent on the substituents and the chirality of the helicene core.816
A diazahelicene radical was reported in 2012 by Takui,
Morita, et al.805 In their approach, the 135.3c cation was
deprotected by using a multistep sequence consisting of
quaternization, Homann elimination, and acidolysis of the
vinyl substituents. The resulting neutral species 135.5 was
resolved into enantiomers on a chiral HPLC column, and
oxidized with PbO2 to yield the chiral, congurationally stable
radical 135.6. The enantiomers of 135.6 were investigated in
detail using ESR, ENDOR, and CD spectroscopic methods.
The synthesis of singly N-substituted helicene cations (e.g.,
135.9) was subsequently explored by Lacour et al., who
developed two alternative routes, each involving a quinacridinium intermediate (135.7 or 135.8) and a hydrazine-mediated
cyclization in either the rst or the second step.806 In each
approach, an excess of hydrazine or amine was used to eect
the cleavage of the NN bond.
The synthesis of the dioxa analogues of 135.3, chromenoxanthene cations 135.13, was achieved in 2010 by Lacour and
co-workers.807 In the optimized reaction sequence, the reduced
neutral species 135.12 was rst obtained by partial
demethylation of 135.2a, followed by thermal cyclization of
the resulting mixture of xanthen-9-ylium cations and hydrogenation with NaBH4. 135.12, which could be separated into
enantiomers by means of chiral HPLC, was quantitatively
converted into 135.13 by oxidation with diiodine. 135.13 was
unstable and was gradually converted into the trioxatriangulenium cation 77.3a upon heating.
5.2.3. 1,4-Diheteraphenalenoids. The quinolino[4,3,2kl]acridine system 136.2, structurally related to the pyridoacridines described above, was synthesized by Mitchell and Rees817
and Stevens et al.818 from the benzotriazole 136.1, using,
respectively, photochemically and thermally induced variants of
the GraebeUllmann synthesis (Scheme 136). The reaction is
quite general, and a range of substituted derivatives could be
obtained. 136.2 and its derivatives were explored for their
antitumor properties by the Stevens group, who developed
alternative synthetic protocols based on radical cyclizations and
Pd-catalyzed couplings.819825 Related pentacyclic systems,
136.35, were obtained by Katritzky et al. in a modied
synthesis involving corresponding dihydroacridines, xanthenes,
and thioxanthenes (136.6).826 136.4 was also obtained in low
yield in a direct coupling reaction between benzotriazole and
xanthene.827 Alajar n et al. reported the synthesis of the
hexacyclic system 136.10, which was obtained from 136.7 in an
attempted bisannulation of the transient ketenimine 136.8.828
The desired bisannulated product 136.9, which formed
alongside 136.10, could be reductively cyclized to yield
136.10. A structurally distinct 1,4-diheteraphenalenoid, komarovidinine 136.12, was obtained by Tulyaganov et al. as a
dehydrogenation product of alkaloid isokomarovine, and was
synthesized independently by oxidative cyclization of the carboline 136.11.829 In later work, an N-oxide of 136.12 was
isolated and characterized.830
5.2.4. 1,3a-Diheteraphenalenoids. This heteroatom
pattern is found in a range of fused phenoxazine and
phenothiazine derivatives. In a 1944 work of Gilman and co-
Scheme 136. Syntheses of Quinolino[4,3,2-kl]acridines and

Related Systemsa
a
Reagents and conditions: (a)817 UV irradiation, 254 nm, MeCN,
39%; (b)818 Ph2O, reux, 2 h, 84%; (c)826 (1) n-BuLi, THF, (2) CuI,
reux; (d)827 DDQ, toluene, reux; (e)828 (1) PPh3, toluene, rt, 1 h,
(2) Ph2CCO, toluene, rt, 30 min; (f) H2, Pd/C, EtOH, 60 C, 14
h, 65%; (g) P(OEt)3, o-xylene, reux, 16 h, 30%; (h)829 Pd black,
180200 C, 40 min.
workers, 9H-quinolino[3,2,1-kl]phenothiazin-9-one 137.2 was

synthesized by intramolecular cyclization of two isomeric acyl
chlorides 137.1 and 137.3.831 Fused phenoxazine 137.6a and
its sulfur analogue 137.6b were obtained in 1962 by VanAllan
and Reynolds in a two-step sequence involving intramolecular
acylation of the corresponding nitriles 137.4ab, followed by
dehydrogenation.482 In subsequent work, the carbonyl
reactivity of 137.6ab was explored by the same authors.832
More recently, the group of Lautens described a domino bisannulation leading to the phenoxazine derivative 137.10.833
The reaction combined two bifunctional reactants, 137.7 and
137.8, which were assembled catalytically using norbornene as
a template. It was proposed that the templating eect was
achieved through the formation of a cyclic intermediate 137.9,
which directed the rst Heck-like coupling ortho to the iodo
substituent.
The antitumor activity of quinobenzoxazine834 (A-62176,
138.4, Scheme 138) spurred an interest in fused 3Hpyrido[3,2,1-kl]phenoxazin-3-one derivatives. A general synthetic strategy to these systems (138.3) involves a basecatalyzed double condensation of enamino-ketoacid 138.1
followed by regioselective nucleophilic substitution of one of
the remaining uorines. By employing a range of fused oaminophenols, the research groups of Hurley835,836 and Na837
CX
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Scheme 137. 1,3a-Diheteraphenalenesa
of the 20th century, can be prepared with variable eciency

from a range of anthranilic acid derivatives,838844 or from
indazole838,840 (Scheme 139). A higher yield was achieved in
Scheme 139. Syntheses of Tricycloquinazolinea
Reagents and conditions: (a)841 R = COO(NH4), heat, 0.08%; (b)841

R = COOMe, ammonium benzenosulfonate, heat, 516%; (c)841 R =
CONH2, p-TsOH, heat, 2025%; (d)840,841 R = CN, p-TsOH, 210
230 C, 26%; (e)839 R = CHO, NH4Cl, 1722%; (f)838,840 Cu, 270
290 C, 17%; (g)845 SnCl4, P4O10, xylene, reux, 66%; (h)846 for
139.1: NH4OAc, sulfolane, AcOH, 170 C, 10 h.
a
Reagents and conditions: (a)831 (1) PCl5, xylene, 10 min, rt, (2)
SnCl4, xylene, 45 min, rt; (b)482 HCl, AcOH, reux; (c) Pd/C, pcymene, reux; (d)833 Pd(OAc)2, P(m-chlorophenyl)3, norbornene,
K2CO3, MeCN, 135 C, 18 h.
1959 by Butler and Partridge, who prepared 139.1 by

dehydration of the oligoamide 139.2, thus providing an initial
structural proof.845 Tricycloquinazoline is a thermally stable
compound and easily undergoes electrophilic substitution
reactions.839,845,846 It is highly carcinogenic,841 and a large
number of its substituted derivatives were prepared by
Partridge, Baldwin, et al., with the aim of studying the tumorinducing properties.847851 An improved synthesis of tricycloquinazolines, developed in 1973 by Yoneda and Mera,846
involves heating of substituted anthranils with ammonium
acetate in a mixture of sulfolane and acetic acid. Substituted
derivatives 139.36 obtained in this way were subsequently
functionalized with alkoxy- and alkylthio chains by the groups
of Keinan and Kumar, to yield a new family of discotic liquid
crystals with electron-decient cores.852856 These compounds
are highly uorescent with an emission maximum at ca. 570
nm. An oligoether-substituted TCQ was found to form a Colh
phase that could be doped with up to 10 mol % of potassium,
yielding electron mobilities of 104 cm2 V1 s1 at 150 C.857
A class of TCQ-containing materials was obtained in 2004 by
Faul et al., using ionic self-assembly between the hexahydroxy
derivative of 139.1 and tetraalkylammonium salts.858 The
hexaanionic TCQ tecton was found to produce several types of
self-assembled structures, including a lamellar mesophase with
an interlayer spacing of 2.98 nm.
In the course of their investigations on tricycloquinazoline
and its carcinogenic properties, published mostly in the 1960s,
Partridge and co-workers synthesized a number of related cyclic
amidine derivatives, including isomers of 139.1 (140.7,859
140.9,860 and 140.15861), triaza systems (140.12,493 140.13,493
140.17,861 140.19861), and diazaoxa systems 140.3859,862 and
140.22861,863 (Scheme 140). The synthetic strategies mostly
relied on classical dehydrative condensations and nucleophilic
substitutions, and were generally concise and high-yielding. In
the case of 140.12, the structural ambiguity associated with the
Scheme 138. 3H-Pyrido[3,2,1-kl]phenoxazin-3-onesa
Reagents and conditions: (a)836 NaHCO3, DMF, 100 C, 2.5 h; (b)

amine, pyridine, reux, 36 h.
successfully prepared extended derivatives of quinobenzoxazine

138.59.
5.3. Tri- and Tetraheteraphenalenes
5.3.1. Tricycloquinazolines and Related Systems.

Tricycloquinazoline (TCQ) 139.1, known since the beginning
CY
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Scheme 140. Syntheses of Tricycloquinazoline Analoguesa
Reagents and conditions: (a)859 AcOH, 180190 C, 90 min; (b)860 (1) acetone, 30 min, (2) NH3/EtOH; (c) neat, 210 C, 1 h; (d) (1) NaCl,
AlCl3, 100320 C, 1 h, (2) NaNO3, HNO3 (76% as nitrate), (3) NEt3; (e) (1) POCl3, PCl5, 120140 C, 3 h, (2) 2-aminopyridine; (f)493 NaCl,
AlCl3, 320 C, 1 h; (g)861 neat, 320 C, 15 min; (h) N2H4, Raney Ni, EtOH, 70 C; (i) aniline, reux, 30 min; (j) DMF, aq NaOH, reux, 15 min;
(k)864 H2, Pd/C, EtOH.
a
nal Scholl-type coupling was resolved by a parallel synthesis of

the methyl substituted derivative 140.13.493 In related later
work by Mart nez et al., the formation of N-oxides 140.24 and
140.26 was postulated on the basis of partial spectroscopic
data.864
A dierent approach to tetraazaphenalenoid systems was
developed by Shaw et al.865867 By condensing a substituted
1,3,6,9a1-tetraazaphenalene with various bidentate nucleophiles,
a range of extended nitrogen-rich frameworks were obtained
(C41.13, Chart 41). In 2014, a pentacyclic phenalenoid 141.3
was obtained in a uniquely concise synthesis by Rajanarendar et
al.868 The initial step involved a CAN-mediated multicomponent condensation of isoxazolyl cyanoacetamide 141.1
with malonodinitrile, benzaldehyde, and 2-hydroxyacetophe-
none, and was followed by the closure of the pyrimidinone ring

with acetic anhydride (Scheme 141).
A route to heterahelicene derivatives 142.2 and 142.3 was
developed in 2004 by Okada et al. (Scheme 142).869 Their
strategy involved double intramolecular N-arylations of
appropriate linear precursors, 142.1 and 142.4, which were
performed, respectively, under Pd- and Cu-catalyzed coupling
Scheme 141. Multicomponent Synthesis of a Pentacyclic
Phenalenoida
Chart 41. Extended 1,3,6,9a1-Tetraazaphenalenes
Reagents and conditions: (a)868 CAN, EtOH, 60 C; (b) Ac2O,

reux, 5 h.
a
CZ
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Metzger.873 In 2005, Takahashi and co-workers employed a

chromium-mediated benzannulation to convert N-phenylpyrrole into ullazines 143.5ad in a sequence of two
cyclization steps.874 A concise approach to ullazine derivatives
was reported in 2013 by the Gratzel group,875 who transformed
bisalkynes 143.6 into substituted ullazines (e.g., 143.7) using
the Furstner cyclization/hydride shift reaction.876 Interestingly,
143.7 undergoes VilsmeierHaack formylation with good
regioselectivity, providing convenient access to functionalized
derivatives, such as 143.9ab. The latter two species as well as
a range of their dierently substituted analogues were used as
sensitizers in DSSC devices, yielding power conversion
eciencies of up to 8.4% (for 143.9a).
A number of larger cyclopenta[cd]phenalenes are known,
containing a heterocyclic ve-membered ring. However, no
general synthetic route to such systems has been developed.
POCl3-induced dehydration of two dierent dicarboxylic acids
144.1 and 144.2, carried out in 1943 by Gilman and
Stuckwisch,877 yielded benzo[8,1]indolizino[2,3,4,5,6-defg]acridine-7,11-dione 144.3 (Scheme 144, for an extension of
this approach, see ref 444). In 1983, Grimshaw and Hewitt
reported the formation of the fused triazole 144.5, which could
be induced electrochemically or photochemically.878 The fused
thiophene 144.8 was prepared in 2004 by Hoger et al. in a twostep sequence involving the condensation between sodium 3thienylacetate and pyrylium salt 144.6, followed by double
intramolecular Heck coupling.879,880 144.8 was subsequently
elaborated into the highly functionalized rod-like structure
144.9, which aggregated in solution and on solid substrates.
Interestingly, a similar thiophenephenalene fusion is found in
a classical dye, Indanthrene Blue Green FFB 145.2 (Scheme
145), obtainable via cyclization and dimerization of benzanthrone-3-sulnylacetic acid 145.1.1,464
Ren et al. used the Lewis-acid-activated FriedelCrafts
arylation881 to convert the bis(triazene) precursor 144.10 into
the dibenzoullazine derivative 144.11.882 Extended dibenzoullazines C42.14 were also obtained in a [3+2] cycloaddition
dehydrogenation sequence performed on azaphenalene ylide
126.3 (Chart 42, see also Scheme 126, section 5.1).682 Other
systems containing a hetero cyclopenta[cd]phenalene unit
include arnoamine A (132.15, section 5.2) and the fused
phosphole system 53.14285 described in section 3.2.
Each of the phenalene derivatives discussed above has a
closed-shell conguration in the neutral state. A number of
heteroaromatic phenalene derivatives were developed with the
aim of stabilizing open-shell electronic structures. The prime
example of such a structure is 1,3-diazaphenalenyl, a persistent
neutral radical prepared in 2002 by Morita et al., which
displayed thermally controlled -dimerization in the solid
state.883885 Tetrathio-886 and hexathiophenalenylium887 cations [160.13]+ and [160.15]+ were prepared by Haddon et al.
by multiple substitutions of the respective ketones 144.12 and
144.14 using various sulfur sources. Phenalenyl 160.13 was
obtained by one-electron reduction of the monocation
dimerizes in the solid state with concomitant opening on one
of the disulfur bridges,886 whereas the 160.15 radical has so far
only been observed in solution.884
A thiophene-based bis(phenalene) structure 144.19 was
reported in 2004 by Kubo and co-workers.888 Its synthesis
started with a one-step formation of the central thiophene ring
from acenaphthylene 144.16. The resulting intermediate,
144.17, which formed as a mixture of regioisomers, was
elaborated into the bis(phenalene) precursor 144.18 using a
conditions. An extension of this strategy was later used by the

same group in the synthesis of 2,2:6,2:6,6-trioxytriphenylamine 76.7 (section 4.1).386 A dierent approach to the
synthesis of substituted heterohelicenes, such as 142.6, was
proposed in 2008 by Menichetti and co-workers.870 142.6 was
obtained by direct electrophilic insertion of two sulfur bridges
to the electron rich arylamine 142.5, in a reaction with
phthalimidesulfenyl chloride 142.9. In an analogous reaction,
the benzo[a]phenothiazine derivative 142.7, itself prepared by
electrophilic bridging of an appropriate triarylamine, was
converted into the extended helicene 142.8 in 75% yield.
142.6 and 142.8 were separated into enantiomers by HPLC
using a column packed with an amylose-based chiral stationary
phase. Radical cations of 142.3 and its substituted derivatives
were investigated in 2015 by Menichetti, Viglianisi, et al.871
These radicals could be generated in nearly quantitative yields
using AgSbF6 as the oxidant, and the oxidation process was
electrochemically reversible.
Scheme 142. Triarylamine Heterohelicenesa
Reagents and conditions: (a)869 Pd(dba)2, (t-Bu)3P, t-BuONa,

toluene, reux 2 h; (b)869 CuI, KI, HMPA, 160 C, 16 h; (c)870 2.3
equiv of 142.9, CHCl3, 60 C, 5 h; (d)870 1.5 equiv of 142.9, CHCl3,
60 C, 16 h.
5.4. Phenalenoids with Nonbenzenoid peri-Fusion
5.4.1. Cyclopenta[cd]phenalenes. The synthesis of

ullazine (indolizino[6,5,4,3-ija]quinoline), a four-ring
cyclopenta[cd]phenalene isoelectronic with pyrene, has been
achieved by means of several distinct strategies (Scheme 143).
In the original report by Balli and Zeller, published in 1983,
substituted ullazines 143.2ad were obtained by in situ
deprotection and condensation of the double dithianes
143.1ad.872 A charge-separated valence structure corresponding to an outer [13]annulene anion (143.10) can be drawn for
ullazine, indicating a potential for stabilizing charged states.
Radical cations and anions of 143.1ad were generated and
studied using ESR and ENDOR spectroscopies by Gerson and
DA
Chemical Reviews
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Scheme 143. Ullazinesa
Reagents and conditions: (a)872 HgCl2, MeOH, H2O, reux, 24 h; (b)874 (1) n-BuLi, TMEDA, hexane, 0 C, 1 h, (2) CrCl3, 3-hexyne, 50 C, 12 h;
(c)874 (1) n-BuLi, THF, 78 C, 1 h, (2) CrCl3, (R)2-acetylene, 50 C; (d)875 60% InCl3, toluene, 100 C, 24 h; (e)875 (1) POCl3, DMF, DCE, rt, 2
h, (2) 1 M NaOH, rt, 1.5 h; (f)875 cyanoacetic acid, piperidine, CHCl3, 4 h, 80 C.
a
Scheme 144. Syntheses of Heterocyclic Cyclopenta[cd]phenalenesa
Reagents and conditions: (a)877 POCl3, xylene, rt, 20 min; (b)878 cathode reduction, 2.25 V vs SCE (20%) or h, MeOH (29%); (c)879 Ac2O, 150
C, 2 h; (d)879 PdCl2(PPh3)2, DBU, DMA, 160 C, 12 h; (e)882 BF3Et2O, DCM, rt, 30 min; (f)886 (1) P2S5, toluene, reux, 16 h, (2) HCl (4 M),
reux, 1 h; (g)887 (1) KSAc, DMF, rt, 72 h, 70%, (2) Lawessons reagent, chlorobenzene, 135 C, 36 h, (3) TfOH, 8% (two steps); (h)888 sulfur,
DMF, reux, 2 h, 90%; (i)888 p-chloranil, benzene, reux, 5 min.
a
1.00 V. The latter feature was reected in the electronic

spectrum of 144.19, revealing an extended NIR absorption in
the 8002000 nm range. The redox amphotericity of 144.19
multistep annulation sequence. 144.18 was oxidized with

chloranil to the fully conjugated target 144.19. 144.19 had an
extraordinarily small electrochemical HOMOLUMO gap of
DB
Chemical Reviews
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Scheme 145. Indanthrene Blue Green FFBa
6. NONBENZENOID FUSION
All fused ring systems discussed in the preceding sections
contained at least one benzenoid peri-fusion point, that is, one
combining three conjugated six-membered rings. Such an
arrangement can be denoted 6-6-6 fusion for simplicity. A
large number of nonbenzenoid PHAs exist; however, because of
their considerable structural diversity, they are dicult to
classify. Heteroaromatic circulenes constitute one well-dened
and consistently explored group of molecules, which are
discussed in section 6.1 (Chart 43). The remaining material is
Reagents and conditions: (a)1,464 KOH, NaOCl.
Chart 42. Dibenzoullazines
Chart 43. Classication of Nonbenzenoid Systems Used in

This Sectiona
was manifested in the easy accessibility of reduced and oxidized

species, including dianion, anion radical, cation radical, and
dication. The neutral species had a pronounced biradicaloid
character, with the experimentally determined singlettriplet
gap of ca. 5 kJ/mol.
5.4.2. Cyclohepta[cd]phenalenes. peri-Fusion of a 7membered heterocyclic ring to phenalene was reported by
Franz (Scheme 146).889 By condensing 9-butoxy-1H-phenalen-
Heteroatom placement and -conjugation are not shown.
divided according to the type of peri-fusion present, that is,

according to the sizes of individual fused rings. By far the most
common motif is the 5-6-6 fusion (section 6.2), corresponding
to the parent acenaphthylene hydrocarbon. The 5-5-6-fused
systems and structures containing 7-membered rings are
presented, respectively, in sections 6.3 and 6.4.
Scheme 146. Phenalene-Fused Diazepinea
6.1. Circulenoids and Related Systems
In hydrocarbon chemistry, [n]circulene is a general name for a

ring system in which n angularly fused benzene rings fully
surround an inner n-membered ring. The two most ubiquitous
motifs are those of coronene ([6]circulene) and corannulene
([5]circulene). Circulene hydrocarbons with n = 7,890892
8,893895 and 4896 are also known, but they are signicantly
more dicult to prepare and, consequently, much less explored.
In a broader sense, which follows from the original usage of the
term by Dopper and Wynberg,897 the name circulene refers
to a variety of structurally related molecules containing such
additional features, as heteroatoms, nonbenzenoid peripheral
rings, or nonconvex central polygons, and has also been applied
to systems with incompletely fused periphery (quasicirculenes898). Regardless of these dierences, the central ring
in circulenoid molecules is normally close to planarity. Systems
discussed below have been selected according to this broader
denition of circulene, with the exception of [6]circulenes
containing at least one benzenoid fusion point, which were
discussed in the preceding sections. A number of theoretical
studies on heteroaromatic circulenoids have been reported,
concerning the structure and dynamics of bowl-like systems,899901 cation interactions,902 and boron-containing
circulenes.903 The following discussion is focused on relevant
a
Reagents and conditions:889 (a) o-diphenylamine, 40% HBF4, xylene,
reux, 4 h; (b) toluene, aq NaOH.
1-one 146.1 with o-diphenylamine, the fused 1,4-diazepinium

salt 146.3 was obtained, which was subsequently deprotonated
to the free base 146.4.
DC
Chemical Reviews
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relative to the nonfused dipyrrolyldiketoneboron complex.

Compound 149.13 revealed the formation of three mesophases
on cooling from the isotropic phase, with Colr, lamellar, and
Colh structures, respectively. 149.13 was also found to exhibit
increased electrical conductivity, and an ability to form anionresponsive supramolecular gels.
In 2015, Cao and co-workers reported the synthesis of two
isomeric thiophene-fused corannulenes 150.2 and 150.4, which
were prepared, respectively, from 2- and 3-thienyl-substituted
precursors 150.1 and 150.3, using dierent oxidative coupling
reactions (Scheme 150).914 The OFET performance of 150.2
and 150.4 was tested in the bottom gate/top contact
architecture, showing no eld-eect properties for the 150.4
isomer. In contrast, 150.2 revealed p-type transport properties
with a hole mobility of 0.06 cm2 V1 s1, threshold voltage of
38 V, and a current on/o ratio of 103.
6.1.2. [5]Heteracirculenoids. The synthesis of [5]circulenes with embedded heteroatoms is made dicult by
the need to introduce curvature into the -conjugated
framework, and by potential side reactivity. These points are
illustrated in the attempted synthesis of 1,2-diazadibenzo[d,m]corannulene 151.2 by Bodwell, Scott, et al. (Scheme 151).915
The synthetic plan relied on the use of the pyridazine precursor
151.1, following the eective paths established for dibenzo[d,m]corannulene, the carbocyclic parent system of 151.2.
However, 151.1 was found unreactive under Pd-catalyzed
coupling conditions, possibly as a result of intramolecular
coordination of pyridazine to palladium. Interestingly, attempts
to eect the required ring closures using ash vacuum pyrolysis
led to a rearranged product of N2 elimination, 151.3. In one
mechanistic hypothesis, the diaza product was assumed to form
as an unstable intermediate and subsequently collapse into
151.3 under the harsh conditions of FVP.
In 2015, Ito, Tokimaru, and Nozaki reported the synthesis of
quintuply benzo-fused 6b2-azacorannulene 152.2 (Scheme
152).916 Their strategy relied on the [3+2] cycloaddition of a
substituted diarylacetylene to the fused 9a-azaphenalene ylide
126.3 (section 5.1), generated in situ from the respective 126.2
salt. The resulting fused pyrrole derivative 152.1 was subjected
to a Heck-type triple ring closure, producing 152.2 in moderate
yield. The bowl structure of 152.2 is slightly skewed because of
the presence of the nitrogen atom and the distance of the outer
rim atoms the pyrrole plane varies from 1.38 to 1.73 . The
large size of the bowl enhances stacking interactions, and
convex-to-concave aggregation was observed in the solid-state
packing pattern. Evidence for aggregation in solution was
obtained using 1H NMR spectroscopy, yielding an aggregation
constant of ca. 5.0 M1. 152.2 has a bright yellow color in
solution, with the lowest-energy absorption maximum at 466
experimental work and is organized according to the placement

of heteroatoms and the size of the inner circulene ring.
6.1.1. Heterofused Circulenes. Carbocyclic circulene
motifs with fused peripheral heterocyclic rings are currently
limited to corannulene derivatives (for corannulene-fused
porphyrinoids, see section 7.1). Pentakis(1,4-benzodithiino)corannulene 147.2 was obtained in 2004 by Scott et al. by
exhaustive nucleophilic substitution of decachlorocorannulene
147.1 with 1,2-benzendithiolate (Scheme 147).904 147.2
Scheme 147. Synthesis of Pentakis(1,4benzodithiino)corannulenea
Reagents and conditions:904 (a) 1,2-benzendithiol, NaHCO3, DMF, 3

h, rt.
possesses ve exible aps, which extend the corannulene

cavity, and an assembly of two molecules of 147.2 was found to
encapsulate a benzene molecule in the solid state. On the basis
of this nding, 147.2 was considered as a potential receptor for
C60 fullerene.
A convenient route for corannulene functionalization leads
through the unstable corannulyne 148.2,905 which can be
converted into a variety of DielsAlder adducts, such as the
148.3 endoxide (Scheme 148). The latter compound was
converted into isocorannulenofuran 148.4, using the stetrazine approach,906 as reported in 2006 by Sygula et al.907
148.4 is moderately stable and can be stored for weeks under
inert conditions. It is however a reactive DielsAlder diene and
was successfully applied to the synthesis of benzannulated
corannulene derivatives (e.g., 148.6) as well as corannulenebased molecular clips and tweezers.908911
Corannuleno[1,2-c]pyrrole 149.3 was prepared from nitrocorannulene by Lash and co-workers912 (Scheme 149), as a
precursor to corannulene-fused porphyrins (section 7.1).
Pyrrole 149.3 was subsequently used by Seki, Maeda, et al. to
construct diketoneboron complexes containing one (149.10
13) or two (149.5) corannulene fragments.913 The presence of
the corannulene unit decreases the HOMOLUMO gaps and
signicantly increases chloride and bromide binding constants,
Scheme 148. Chemistry of Isocorannulenofurana
Reagents and conditions:907 (a) NaNH2, t-BuOK, THF; (b) CHCl3, 55 C, 15 min; (c) benzenediazonium-2-carboxylate, 1,2-dichloroethane,
reux; (d) Fe2(CO)9.
DD
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Scheme 149. Chemistry of Corannuleno[1,2-c]pyrrolea
Reagents and conditions: (a)912 [NO2][BF4], MeCN/DCM; (b)912 ethyl isocyanoacetate, THF, 149.14; (c)912 KOH, N2H4, ethylene glycol, 180
190 C; (d)913 malonyl chloride, DCM, 2 h, rt; (e)913 2-R-substituted pyrrole, malonyl chloride, DCM, 2 h, rt; (f)913 BF3Et2O, DCM, rt.
Scheme 150. Thiophene-Fused Corannulenesa
contributions from carbazole-like resonance contributions. The

bowl inversion barrier in 152.2 was not determined
experimentally, but an estimate of 17 kcal/mol was provided
by DFT calculations.
An alternative approach to 6b2-azapentabenzo[bc,ef,hi,kl,no]corannulene was subsequently reported by the group of
Shinokubo.917 Their synthesis started with an oxidative selfcoupling of phenanthrenoamine 152.3, yielding the bis(phenanthro)-fused pyrrole intermediate 152.4. The azacorannulene framework was subsequently completed in three
steps, with the Heck cyclization used in all CC bond-forming
transformations. Finally, in the resulting azacorannulene 152.7,
the 2,4,6-triisopropylphenyl group was installed in two steps,
yielding the fully substituted 152.9. The presence of the bulky
aryl group in 152.9 enabled the experimental determination of
the bowl-inversion barrier using EXSY spectroscopy (23.3 kcal/
mol at 393 K in 1,2-dichlorobenzene-d4). 152.9 easily forms a
NIR-absorbing radical cation in the presence of excess
triuoroacetic acid or upon direct chemical or electrochemical
oxidation. 152.9 was found to interact with C60 in solution,
with an association constant of 3800 M1. This interaction
resulted in partial uorescence quenching in 152.9, and the
appearance of a weak charge-transfer band in the absorption
spectrum at ca. 800 nm. The convexconcave interaction
between 152.9 and C60 was additionally observed in the solid
state, with the shortest van der Waals distance between the
surfaces of 3.29 . The solid-state complex 152.9 C60
exhibited a large local charge mobility of 0.17 cm2 V1 s1,
which was attributed to partial charge transfer and favorable
alignment of molecules in the solid state.
6.1.3. [6]Heteracirculenoids. Systems containing a
benzenoid peri-fusion point (i.e., at least a phenalene
substructure) that would formally t the denition of a
[6]circulene are discussed in the preceding sections. The
remaining structural motifs contain the triphenylene substructure and have been mostly developed as heteroaromatic
analogues of sumanene. In an initial attempt to make
trithiasumanene 153.7, Klemm and co-workers used a catalyzed
Reagents and conditions: (a)914 DDQ, MSA, CH2Cl2, 0 C, 10 min;

(b)914 FeCl3, Et2O, DCM, rt, 30 min.
a
Scheme 151. Attempted Synthesis of 1,2Diazadibenzo[d,m]corannulenea
Reagents and conditions: (a) Pd-mediated coupling; (b) ash

vacuum pyrolysis, 1520%.
a
nm, and shows blue-green uorescence (max = 490 nm, F =

0.24). On the basis of NICS calculations, it was proposed that
the conjugation in 152.2 is principally described by assigning
Clar sextets to all of the outermost benzene rings, with minor
DE
Chemical Reviews
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Scheme 152. 6b2-Azapentabenzo[bc,ef,hi,kl,no]corannulenea
Reagents and conditions: (a)916 DMSO, N,N-diisopropylethylamine, 100 C, 17 h; (b)916 Pd(PCy3)2Cl2, Cs2CO3, DMA; (c)917 DDQ, TFA,
toluene, rt, 1 h; (d)917 Pd(OAc), PCy3HBF4, K2CO3, DMA, 130 C, 43 h; (e)917 Br2, CCl4, 70 C, 12.5 h; (f)917 Pd(OAc)2, PCy3HBF4, K2CO3,
DMA, 130 C, 16 h; (g)917 bis(pinacolato)diboron, [Ir(OMe)cod]2, 4,4-di-tert-butyl-2,2-bipyridyl, octane, 10.5 h, 110 C, 80% yield; (h)917 2bromo-1,3,5-triisopropylbenzene, PdCl2(dppf)CH2Cl2, Cs2CO3, 1,4-dioxane, 13 h, 100 C.
a
Scheme 153. Synthesis of Trithiasumanenea
Reagents and conditions: (a)918 H2S, Harshaw C4-0101 T catalyst, 500 C; (b)919 NBS (3 equiv), DMF, rt; (c)919 trimethylsilylacetylene,
Pd(PPh3)4, CuI, NEt3, reux; (d)919 conc. HCl, AcOH, 80 C; (e)919 1000 C, 0.005 Torr, N2 ow.
a
SnMe2, and GeMe2 units were prepared by Saito et al. using

stepwise lithiation and electrophilic bridging of triphenylene,
but trithiasumanene was not accessible using such an
approach.922924 A successful route to substituted trithia- and
triselenasumanenes (154.4 and 154.6, Scheme 154) was
developed in 2014 by Shao et al.925,926 These compounds
were obtained from hexabutoxytriphenylene 154.1, which was
directly lithiated and reacted with elemental sulfur or selenium,
to yield expanded sumanenes containing one or two
dichalcogen bridges (154.2 and 154.5). The latter compounds
were contracted to the desired sumanenes by means of a Cumediated chalcogen extrusion. This reaction, which was run
without the use of a solvent, is an ecient means of strain
induction and provides multigram amounts of 154.4 and 154.6.
Triselenasumanene 154.6 has a smaller bowl depth (0.47 )
than its trithia congener and shows ecient columnar stacking
in the solid state. The presence of S and Se heteroatoms in
154.4 and 154.6 leads to a narrowing of HOMOLUMO gaps
gas-phase reaction between triphenylene and hydrogen sulde

(Scheme 153), which however only yielded trace amounts of
triphenyleno[1,12-bcd:4,5-bcd]dithiophene 153.2.918 The
rst successful synthesis of trithiasumanene, reported by
Otsubo et al. in 1999,919 started with benzotrithiophene
153.3, which was converted into a regioisomeric mixture of
tris(1-chlorovinyl) derivatives 153.6. The latter mixture was
subjected to ash vacuum pyrolysis (FVP), producing 153.7 in
35% yield. Interestingly, FVP was not useful for the synthesis of
the parent hydrocarbon sumanene attempted in 1993 by Mehta
et al.920 Sumanene was obtained in 2003 by Sakurai, Daiko, and
Hirao by means of a nonpyrolytic method.921 The bowl-shaped
molecules of trithiasumanene 153.7 have a depth of ca. 0.79
and show ecient convexconcave stacking in the solid state.
The principal diculty in synthesizing 153.7 lies in the high
internal strain of the bowl, which must be energetically
compensated during the cyclization process. Strain-free
sumanene derivatives containing combinations of S, SiMe2,
DF
Chemical Reviews
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Scheme 154. Chemistry of Substituted Trithia- and Triselenasumanenesa
a
Reagents and conditions: (a)925 n-BuLi, TMEDA, 60 C; (b)925 sulfur, 78 C to rt; (c)925 Cu powder (10 equiv), 200 C; (d)925 Se powder, 78
C to rt; (e)927 Oxone, THF/H2O, rt, 2 h; (f)927 (1) NaOH, EtOH/H2O, reux, 2 h, (2) aq HCl, (3) Ac2O, reux; (g)927 2-aminopyridine, DCC,
THF, reux.
Scheme 155. Synthesis of Triazasumanenesa
relative to the all-carbon sumanene. The electron-rich

sumanenes 154.4 and 154.6 undergo oxidative opening of
one of the benzene rings, to yield diesters 154.7 and 154.8
(Scheme 154). 927 The diesters were cyclized to the
corresponding anhydrides 154.9 and 154.10, which were
converted into imides 154.11 and 154.12. The presence of the
expanded, 7-membered ring in the latter imides results in
completely planar structures, which show tight stacking in
the solid state. In comparison with 154.4 and 154.6, the [5-67]-fused systems are distinguished by red-shifted absorptions
and emissions, and high uorescence quantum yields.
Even though not fully conjugated, the triazasumanenes 155.5
and 155.6 (Scheme 155), reported by Higashibayashi, Sakurai,
et al., are of interest for preparative and structural reasons.928
The synthetic route follows the strategy established in the
original sumanene work,921 and includes Pd-catalyzed cyclotrimerization, ring metathesis, and aromatization stages. The
metathesis involves hydrolytic opening of lactam bonds in
155.2, followed by cyclization induced by pentauorophenyl
diphenylphosphinate. The bowl-shaped lactam 155.3 could not
be directly dehydrogenated and had to be transformed into the
thioimidate 155.4 prior to aromatization. The thioimidate was
converted into 155.5 using triphenylmethyl uoroborate as an
oxidant. The unique feature of the triazasumanene synthesis is
the enantiospecicity of the entire reaction sequence, which
translates the point chirality of the enantiopure starting
material, 155.1, into the bowl chirality of the sumanene
product. Because of the greater depth of the bowl, caused by
the shorter CN bond distances, the barrier to inversion in
155.5 (over 40 kcal/mol) is much higher than in all-carbon
sumanene, making the triaza structure congurationally stable
at room temperature.
6.1.4. [7]Heteracirculenes. The rst example of a
heteroaromatic quasi-[7]circulene was provided in 1969 by
Zander and Franke,929 who cyclized 5,10-dihydrocarbazolo[3,4c]carbazole 156.1, using the chloroaluminate method, to obtain
the cycloheptanaphthodiindole 156.2 (Scheme 156). In the
1970s, Wynberg and co-workers used an analogous strategy to
prepare a series of thiophene-containing quasi-[7]circulenes
157.2, 157.3, 157.69 (Scheme 157).246,930 The chloroaluminate method was found to be more ecient than dehydrogen-
Reagents and conditions:928 (a) Pd(OAc)2, PPh3, [Bu4N][OAc],

Na2CO3, molecular sieves 4 , 1,4-dioxane, 100 C, 2 h, 57%; (b) (1)
12 M HCl, AcOH, 60 C, 3 h, (2) C6F5OP(O)Ph2, N,Ndiisopropylethylamine, DMF, 060 C, 59% (two steps); (c)
Lawessons reagent, 1,2-dichloroethane, microwave, 160 C, 40 min,
92%; (d) triuoroacetic acid, microwave, 100 C, 2 h, 88%; (e) MeI,
K2CO3, DMF, 30 C, 3 h, 79%; (f) [Ph3C][BF4], DTBMP, CH2Cl2,
25 C, 8 h, 73%; (g) m-CPBA, CH2Cl2, 0 C then 15 C, 2 h, 90%,
PMB, p-MeOC6H4CH2; DTBMP, 2,6-di-tert-butyl-4-methyl-pyridine;
Lawessons reagent, 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulde; m-CPBA, 3-chloroperoxybenzoic acid.
Scheme 156. Synthesis of 5,10-Dihydrocarbazolo[3,4c]carbazole929a
Reagents and conditions: (a) phenylhydrazine, aq NaHSO3, reux;

(b) NaClAlCl3, 140150 C.
DG
Chemical Reviews
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Scheme 158. Synthesis of Sulower and Related Systemsa
Scheme 157. Thiophene-Containing [7]Circulenes and

Quasi-[7]circulenesa
a
Reagents and conditions: (a)932 LDA (16 equiv), sulfur (16 equiv),
rt, 24 h; (b)932 aq HCl; (c)932 vacuum pyrolysis (80% yield of 158.3
over three steps); (d)933,934 LDA (16 equiv), selenium (16 equiv), rt,
24 h (50% yield of 158.4 over three steps).
cm2 V1 s1.933 STM investigations performed at the solvent

highly oriented pyrolytic graphite (HOPG) interface revealed
the ability of these heteracirculenes to stabilize the chickenwire 2D polymorph of trimesic acid, and their propensity for
self-aggregation.935 2D crystallization of 158.3, 158.4, and
C16S5Se3 on a Au(111) surface revealed a considerable
dependence of the self-assembly behavior on molecular
symmetry.936
1,4-Naphthoquinone treated with strong acids undergoes
self-condensation into a number of products including
tetrabenzotetraoxa[8]circulene 159.1 (Scheme 159). Such
condensations were already investigated in 1881,937 but 159.1
was rst isolated in 1933 by Erdtman,938 who proposed a
structure of the corresponding [6]circulene analogue (tribenzotrioxasumanene). The correct structure of 159.1 was elucidated
35 years later by Erdtman and Hogberg.939 p-Benzoquinones
reacted similarly (159.24, Scheme 159),940942 but practicable yields were only obtained for substituted reactants (R
H). In the solid state, the tetraoxa[8]circulene core is planar
and relatively strain-free,943 as shown in an X-ray study by Berg
et al. The acid-catalyzed condensation of quinones involves
isolable helicene-like intermediates, such as 159.5, which were
successfully used in stepwise syntheses of unsymmetrically
fused circulenes such as 159.6944 (Scheme 159). In a related
synthesis, naphthoquinone 159.7 yielded an incompletely
characterized circulene, with a structure of 159.8 or 159.8.945
The interest in tetraoxa[8]circulenes was renewed with the
development of their soluble derivatives. In 2000, Christensen
et al. synthesized a series of octasubstituted circulenes (C44.1
5, Chart 44), containing long alkyl chains (C7C11).947 These
compounds were made in 1156% yields by using BF3Et2O in
dichloromethane. C44.14 showed mesomorphic behavior,
but the mesophases were not structurally characterized. In a
related study, the same group prepared a family of indanonebased tetraoxa[8]circulenes.948 Using an analogous method,
Rathore and Abdelwahed synthesized bicycloalkane-annulated
derivatives C44.6 and C44.7, which formed isolable cation
radical salts upon oxidation.949 The respective cations showed
NIR absorptions extending beyond 1100 nm. C44.5, and
hybrid benzo-fused derivatives C44.811, obtained by cross-
Bonds formed by cyclodehydrogenation or cycloaddition are

indicated in red. Reagents and conditions: (a)246,930 AlCl3, benzene;
(b)247,897 NaClAlCl3, 140 C; (c)247,897 maleic anhydride, chloranil;
(d)247,897 Cu, quinoline.
ation by means of aluminum chloride in benzene. These

systems served as precursors to completely fused thiacirculenes
157.5, 157.1012, which were prepared by oxidative cycloaddition of maleimide followed by decarboxylation.247,897 In a
related study, compound 157.1 was found to undergo an
electrophilic cyclization to a [8]circulenoid structure containing
an sp3 carbon in the inner ring.931
6.1.5. [8]Heteracirculenes. Octathia[8]circulene 158.3,
synthesized in 2006 by Nenajdenko et al.,932 is the most
heteroatom-abundant circulene reported to date (Scheme 158).
With its elemental formula C16S8, the compound is a binary
carbonsulfur compound, and it was nicknamed sulower, to
highlight its high sulfur content and unique molecular
geometry. 158.3 was eciently synthesized by pyrolyzing the
octathiol precursor 158.2, which was prepared from the
tetrathiophene 158.1 by exhaustive lithiation of all positions,
followed by sulfurization. Sulower 158.3 is a dark red solid,
insoluble in common organic solvents, and was characterized by
a variety of solid-state techniques, including X-ray crystal
analysis. The mixed seleniumsulfur analogue 158.4 was
prepared using an analogous procedure, in which elemental
sulfur was replaced with selenium.933,934 In the latter synthesis,
partial scrambling of heteroatoms occurred, yielding C16S3Se5
and C16S5Se3 circulenes as side products. 158.3 and 158.4 were
explored as p-type semiconductors in organic eld-eect
transistors, showing limited hole mobilities of up to 9 103
DH
Chemical Reviews
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Scheme 159. Synthesis of Tetraoxa[8]circulenesa
Reagents and conditions: (a) AlCl3, nitrobenzene; (b)945 benzenesulfonic acid melt, 60 C; (c)946 BF3Et2O, DCM, 50%, mixture of isomers; (d)946
AlCl3, benzene.
a
Chart 44. Tetraoxa[8]circulenes
Scheme 160. Synthesis of Azatrioxa- and

Diazadioxa[8]circulenesa
Reagents and conditions: (a)951 chloranil, BF3Et2O, DCM; (b)952

BF3Et2O, DCM.
a
employed for the synthesis of azatrioxa[8]circulenes (160.3

4),952 and was subsequently extended into a stepwise method
enabling the synthesis of unsymmetrically substituted derivatives.953 The introduction of nitrogens was found to produce
red shifts in the absorption spectra and was also reected in the
lowering of the rst oxidation potential. The eect is opposite
to that induced by peripheral benzo fusion, which was observed
to yield blue-shifted electronic absorptions. For the azacontaining circulenes, as well as for its tetraoxa parent, an
antiaromatic contribution was postulated for the central
cyclooctatetraene ring, on the basis of the center NICS(0)
value, which was not in line with the predicted additivity
scheme.951,952
Tetrathia- and tetraselena[8]circulenes 161.2 and 161.3 were
obtained by Wong et al.,954 using a strategy reminiscent of
Nenajdenkos route932 to octathia[8]circulene 158.3. Compounds 161.2 and 161.3 were synthesized from tetraphenylene
161.1 by lithiumbromine exchange followed by reaction with
elemental sulfur and selenium, respectively. The resulting
polychalcogen intermediates were thermally dechalcogenated
condensation of the corresponding benzo- and naphthoquinone, were investigated as uorescent components for OLEDs
by Pittelkow and co-workers.950 These systems showed
moderate to high uorescence quantum yields, dual uorescence decays, and multiple electrochemical reduction and
oxidation events. Blue-emitting OLEDs fabricated using these
materials showed light intensities up to 276 cd m2 at 10 V
(C44.9).
Condensation of tert-butyl-p-benzoquinone yielded a mixture
of regioisomeric tetra(tert-butyl) circulenes, from which the two
major isomers, 159.9 and 159.10, could be isolated (Scheme
159).946 The mixture could be easily dealkylated to provide the
parent 159.2 in excellent yield. Unexpectedly, both 159.9 and
159.10 revealed a strong, cooperative aggregation in solution.
This eect was proposed to be driven by CH rather than
interactions.
Diazadioxa[8]circulenes (160.12) were prepared in 2013
by Pittelkow et al. by oxidative condensation of 3,6dihydroxycarbazoles (Scheme 160).951 A similar approach was
DI
Chemical Reviews
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cycles. In a 1973 report by Hogberg, tetraphenylenotrifuran

162.2 was obtained by fusing the helicene precursor 162.1 with
sodium chloroaluminate at 140 C (Scheme 162).958 Rajca et
al. explored analogous ring closures in a number of [7]helicenes, which yielded the corresponding quasi[8]circulenes
(162.4, 162.6, and 162.8, Scheme 162).898 In addition to tinand palladium-mediated couplings, compounds 162.6 and
162.8 could be eciently obtained by pyrolysis carried out in
a dierential scanning calorimeter. Interestingly, an attempt to
deprotect compound 162.9 using triuoroacetic acid produced
small amounts of the respective quasicirculene 162.10.959
A class of heteroatom-bridged tetraphenylenes, structurally
related to [8]circulenes, was recently developed by Wong et
al.960,961 Starting from tetrasubstituted tetraphenylene derivatives 163.1 and 163.3, these authors successfully prepared
systems containing O, N, S, and Se bridges (163.2, 163.49),
using a variety of metal-mediated coupling strategies (Scheme
163). As a consequence of bridging, the puckering of the
central cyclooctatetraene ring in these systems is reduced
relative to the bridge-free tetraphenylene, but the geometries
remain saddle-shaped. The uniquely high planarization of the
163.4 derivative was explained by the steric eect of the phenyl
substituent. In all cases, the heteroatom bridges contribute to
the -electron conjugation, leading to observable reductions of
HOMOLUMO gaps. With an estimated HOMO energy of
5.78 eV and favorable packing in the crystal, compound 163.4
is a candidate for a p-type semiconductor. The lowest-energy
electronic absorptions are shifted by up to 16 nm relative to the
heteroaromatic monomers (e.g., dibenzofuran, etc.), indicating
a moderate eect of inner cyclic conjugation on the electronic
structure of these bridged systems.
An [8]circulenoid containing six thiophene rings (164.4) was
constructed by Cu-mediated coupling of dithieno[3,4-b:3,4d]thiophene (164.1) by Nishinaga, Iyoda, et al. (Scheme
164).962 Sulfone and silane analogues, 164.5 and 164.6, were
assembled using the same strategy. Similarly to other
[8]circulenoids, these systems contain a highly planarized
cyclooctatetraene (COT) ring, with the deviation from
planarity increasing in the order 164.6 > 164.5 > 164.4. The
authors showed that the increased planarity of the COT ring
leads to a narrowing of the HOMOLUMO gap and to a
concomitant enhancement of paratropicity. Amphoteric redox
behavior was demonstrated for 164.3 and 164.6, both of which
could be chemically converted into the corresponding radical
cations, radical anions, and dianions. A related system, 164.7,
containing only four fused rings, is also planar and was shown
to exhibit enhanced antiaromatic characteristics in comparison
with 164.4.963 A derivative of 164.4 (with R = TIPS-ethynyl)
was successfully tested as a single-crystal eld-eect transistor,
showing hole and electron mobilities of up to 0.40 and 0.18
cm2 V1 s1, respectively.964
6.1.6. Larger Systems. Circulenoids containing an inner
ring larger than 8-membered are currently unknown, and this
limitation may be due to steric reasons. (An unusual, and
apparently highly strained, cyclic helicene derivative containing
an incompletely conjugated inner 9-membered ring was
reported by Maiorana et al.965) The circulene structural
paradigm can be thought to encompass systems in which the
fused ring periphery encloses a nonconvex polygon, typied by
the hydrocarbon kekulene (165.1, Scheme 165). The successful
synthesis of 165.1 by Staab and Diederich966 spurred an
interest in its heterocyclic analogues,967,968 but the majority of
structures reported to date, such as Bells torands 165.2 and
using copper powder to yield the desired products in moderate

yields. The aromatic core of 161.2 is completely planar in the
solid state, whereas the tetraselenium analogue 161.3 reveals a
slight saddle-like distortion from planarity. A complementary
method was developed in 2015 by Miyake et al., in which
variously substituted tetrathia[8]circulenes 161.6 were obtained
by quadruple benzannulation of a borylated cyclothiophene
precursor 161.5.955 161.6 showed a strong dependence of
intrinsic hole mobilities, measured using TRMC, on peripheral
substitution. Highest values (up to 2.66 103 cm2 V1 s1)
were observed for alkyl-substituted derivatives, which were
thought to promote -stacking in the solid state.
A dierent strategy was employed by Tanaka, Osuka, et al. in
their synthesis of tetrabenzotetraaza[8]circulene 161.8.956 The
latter species was obtained from a cyclophane precursor 161.7,
which was subjected to a fold-in-type957 oxidative coupling.
Despite the planar geometry of 161.8, the central cyclooctatetraene ring showed a signicantly reduced antiaromatic
character, consistent with the radialene-like valence formulation
of the circulene. 161.8 has a sharp absoprtion spectrum with
the lowest energy band at 413 nm, and reveals strong
uorescence emission (F = 0.55 in THF) with a very small
Stokes shift (175 cm1), consistent with insignicant reorganization in the excited state.
A number of incompletely fused [8]heteracirculenes are
known. The dehydrogenative cyclization of helicenes, described
above for [7]circulenes, is also eective in closing 8-membered
Scheme 161. Synthesis of Tetrathia- and
Tetraselena[8]circulenesa
a
Reagents and conditions: (a)954 n-BuLi, sulfur; (b)954 n-BuLi,
selenium; (c)954 Cu powder, 250 C; (d)955 HBpin, [Ir(OMe)
(cod)]2, dtbpy, hexane, 10 C, 90 h; (e)955 alkyne, [Cp*RhCl2]2,
Cu(OAc)2H2O, LiOAc, DMF, air, 100 C, 2 h; (f)956 DDQ,
Sc(OTf)3, toluene, reux, 3 h.
DJ
Chemical Reviews
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Scheme 162. Synthesis of Quasi-[8]heteracirculenesa
Reagents and conditions: (a)958 NaClAlCl3, 140 C; (b)898 Pd[P(t-Bu)3]2, K3PO4, toluene, 80 C; (c)898 pyrolysis (DSC scan); (d)898 (nBu)3SnH, AIBN, toluene, reux; (e)959 TFA, CHCl3, 45 min, 0 C.
Scheme 163. Synthesis of Heteroatom-Bridged

Tetraphenylenesa
Scheme 164. Synthesis of Thiophene-Containing

[8]Circulenoidsa
Reagents and conditions:962 (a) (1) LDA, (2) TMSCl; (b) (1) nBuLi, (2) CuCl2; (c) TBAF.
In 2013, Mysliwiec and Step ien reported the synthesis of

chrysaorole 166.2 (Scheme 166), a jellysh-shaped molecule
named after the Chrysaora genus, which was synthesized via
triple intramolecular Yamamoto coupling performed on a
halogenated carbazolophane 166.1 (see section 7.7).971 The
synthesis of 166.2 was designed as a model of the fold-in
strategy, in which the aromatic cyclophane subunits were folded
toward the interior of the macrocycle (Scheme 166, green
arrows), yielding a belt structure with bowl-like curvature. More
generally, the fold-in reaction can be dened as a transformation of a macrocyclic precursor, which results in the
formation of an additional macrocyclic circuit that is smaller
than that originally present in the precursor. The fold-in
concept957 is a versatile synthetic approach that works with
various reaction types and enables the construction of bowlshaped,971973 planar,973 and contorted894 systems, including
carbocyclic894,973 and incompletely conjugated972 aromatics.
166.2 is an unusual bowl-like structure, containing an inner
opening, and has a bowl depth of 1.96 . For the unsubstituted
166.2 (R = H), the internal strain energy of 53.4 kcal/mol was
a
Reagents and conditions:960,961 (a) Pd(PPh3)4, K3PO4, DMF, 140
C, 68%; (b) PhNH2, Pd2(dba)3, t-BuONa, (t-Bu)3P, toluene, 120 C,
85%; (c) CuI, NaN3, DMEDA, DMSO, 120 C, 45%; (d) NaH, BnBr,
THF, 020 C, 85%; (e) (1) n-BuLi, I2, THF, (2) CuI, K2S, DMEDA,
MeCN, 140 C, 69%; (f) n-BuLi, Se, THF, 67%; (g) Cu powder, 250
C, 100%.
165.3,969 were not completely conjugated. Two notable

examples of fully conjugated torands include compound 165.4,
mentioned in Bells PAC review,969 and 3,9,15,19,21,23hexaazakekulene 165.9, reported by Demeunuyck et al.970
The latter compound was assembled from proavines 165.5
and 165.8 using a stepwise acid-catalyzed condensation
protocol. 165.9 is insoluble in common organic solvents, but
it is partly solubilized by strong acids, such as TFA or MSA.
DK
Chemical Reviews
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Scheme 165. Chemistry of Large Circulenoidsa
Reagents and conditions:970 (a) paraformaldehyde (0.5 equiv), 12 N HCl, 3 weeks; (b) NaOH, EtOH; (c) paraformaldehyde (2 equiv), 12 N HCl,
1 week.
Scheme 166. Chrysaorolesa
Scheme 167. Reactions of Acenaphthoquinones with

Aminesa
Reagents and conditions: (a)974 AcOH, reux, 3 h; (b)975 AcOH or

EtOH, reux.
derivative of aceanthra[1,2-b]quinoxaline 167.4, reported in

1911 by Liebermann and Zsua.975 Further examples were
provided by Buu-Ho and Jacquignon976 (C45.1, Chart 45),
Klingsberg and Lewis977 (C45.24), and Amer et al.978,979
(C45.613 and several related 1,2,4-triazine-fused systems).
Acenaphtho[1,2-b]quinoxaline derivatives C45.1416 were
synthesized in 2014 by Nurulla et al. and subjected to
electrochemical polymerization.980,981 As a result, low-bandgap
polymers were obtained, which showed electrochromic switching in the NIR range.
Compounds C45.1718 were reported in 2011 by Kwon,
Kim, et al. as red light emitting materials for use in OLED
devices.982 These materials, obtained by Pd-catalyzed amination
of C45.4, showed good thermal stability with glass transition
temperatures above 140 C. The dipolar characteristic of the
quinoxaline derivatives resulted in prominent solvatochromic
eects. OLED devices based on C45.17 showed maximum
Reagents and conditions:971 (a) [Ni(cod)2], 1,5-cyclooctadiene, 2,2bipyridyl, DMF/toluene, 85 C, 18 h; (b) H2, PtO2, CH2Cl2, 20 C.
estimated by DFT calculations on the basis of a homodesmotic

reaction. By extending the fold-in synthesis to a nonconjugated
cyclophane 166.3, hexahydrochrysaorole 166.4 was synthesized, revealing congurational stability of the bowl in solution.
6.2. Fused Acenaphthylene Derivatives
6.2.1. Hetero[a]fused Acenaphthylenes. Straightforward

access to heterofused acenaphthylenes is provided by
condensation reactions of acenaphthoquinone and aceanthrylene-1,2-dione with aromatic diamines (Scheme 167). Early
examples include acenaphtho[1,2-b]quinoxaline (167.2), prepared in 1899 by Ampola and Recchi,974 and a methyl
DL
Chemical Reviews
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Chart 45. Acenaphthylene-Based Quinoxalines
Chart 46. Acenaphtho[1,2-b]quinoxaline Ligands and Complexes
band at 500950 and 6001300 nm, respectively. Thin lms of

C45.21ab yielded n-channel OFETs with electron mobilities
of up to 0.12 cm2 V1 s1, and BHJ solar cells with power
conversion eciencies reaching 1.8%. Polymers C45.22ab
showed crystalline ordering in thin lms and yielded
considerably improved electron mobilities of up to 0.3 cm2
V1 s1.
Acenaphtho[1,2-b]quinoxalines have found use as extended ligands for transition metals. In 2000, Ji et al.
reported the -expanded phenanthroline C46.1 and its
ruthenium complexes C46.46 (Chart 46).985 In contrast to
C46.6, which was nonemissive, complexes C46.4 and C46.5
brightness of 17 523 cd/m2 and current eciency of 4.55 cd/A

(CIE coordinates x, y = 0.56, 0.43). Further examples of
acenaphtho[1,2-b]quinoxaline structures, developed as potential OLED emitting layers (C45.1920), were provided in
2013 by Bunz, Hamburger, et al.564 Also in 2013, Jenekhe and
co-workers reported the use of tetraazabenzodiuoranthene
diimides C45.21ac and the corresponding polymers
C45.22ab as n-type semiconductor materials.983,984 The
introduction of electron-donating thienyl R groups in
C45.21ab was found to produce red-shifted charge-transfer
bands in the region of 460700 nm. This eect was particularly
remarkable in polymers C45.22ab, which displayed the CT
DM
Chemical Reviews
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Scheme 169. Acenaphthylene-Based Cavitanda
displayed bright luminescence in acetonitrile but were only

weakly luminescent in water solution. C46.4 and C46.5 were
found to bind to calf thymus DNA (CT-DNA), with intrinsic
binding constants of 7.6 104 and 8.8 104 M1, respectively.
These relatively low anities were explained in terms of the
geometric requirements of the C46.1 ligand. In the case of
C46.6, the interaction had a nonintercalative character.
Analogous work was subsequently performed on ruthenium(II)
complexes C46.810 of the benzologous ligand C46.2.986,987
Further luminescent complexes containing the C46.1 ligand are
the copper(I) species C46.7, reported in 2009 by Zhang et
al.,988 and a ReI(CO)3Br complex of Li and co-workers.989 An
asymmetric pyridineimidazole ligand C46.3 and its
ruthenium(II) complexes C46.1112 were synthesized in
2013 by Liu and Zhang.990 Both complexes were found to
intercalate into DNA and induce singlet-oxygen photocleavage
under irradiation at 365 nm. These systems were further
observed to be ecient inhibitors of DNA topoisomerase I.
Alkoxy-substituted benzopyrazine-fused tetracenes 168.45
(TBPy) and their disuldes 168.67 (TBPyS) were designed
by Matsuo et al. in 2013 (Scheme 168).991 The introduction of
Reagents and conditions:992 (a) H2, Raney Ni, toluene, 45 C; (b)

acenaphthenequinone, THF, AcOH, reux, 6 h.
-Expanded uoranthene derivatives, reported by Buu-Ho

and co-workers (Chart 47), include the carbazole system
Chart 47. [k]Fused Fluoranthenes
Scheme 168. Benzopyrazine-Fused Tetracenesa
C47.1, obtained from uoranthene via Haworth-type annulation, Fischer indolization, and aromatization,993 and the three
fused systems C47.24,994 all derived from 8-aminouoranthene. [k]Fused pyrylium salts C47.5 were reported by
Shenbor and Azarov in 1979.995 Furans and oxazoles, such as
C47.67, were obtained in 1982 by Shechter et al. via thermal
and photochemical additions of acetylenes and nitriles,
respectively, to diazoacenaphthenone and 2-diazoaceanthrenone.745
Diacenaphtho[1,2-b:1,2-d]thiophene C47.8 is a red-colored
solid obtained surprisingly simply by fusion of acenaphthene
and sulfur. The reaction, which also works with substituted
acenaphthenes (see Scheme 144, section 5.4), was originally
reported in 1903 by Dziewonski,996 although it was apparently
discovered 10 years earlier, as subsequently claimed by
Rehlander.997 C47.8 can alternatively be prepared by reuxing
167.1 with P4S10 in toluene.998 The compound is of interest
because of its diverse reactivity in cycloaddition reactions.9991001 The pyrrole analogue of C47.8, N-substituted
diacenaphtho[1,2-b:1,2-d]pyrrole C47.9, was synthesized in
2011 by Kawase et al. via a two-step annulation procedure,
starting from 1,2-dibromoacenaphthylene1002 (an earlier synthesis of a substituted variant of C47.9 is shown in Scheme 144,
Reagents and conditions: (a)991 AcOH/EtOH, reux, 13 h; (b) S8,

excess, >200 C, 659 h.
the disulde group was achieved by heating with an excess of

elemental sulfur above 200 C. These derivatives featured NIR
absorptions (onset up to 820 nm), improved photooxidative
stability relative to tetracene, and solution processability. OFET
devices fabricated from 168.47 showed performance
characteristics dependent on the substitution pattern and
fabrication method. Hole mobilities up to 1.7 102 cm2/V
s (with Vth = 30 V and ION/IOFF = 104) were obtained for
thin-lm OFET devices based on 168.7.
A deepened acenaphthylene-fused cavitand 169.3, with a
cavity ca. 14 in length, was reported by Rebek et al. (Scheme
169).992 In their synthesis, the octanitro cavitand 169.1 was
reduced to the octaamine 169.2, which was then condensed
with acenaphthoquinone to yield 169.3. While the binding
constant of 169.3 toward C60 was relatively low (900 250
M1 in toluene), the cavitand showed good selectivity, because
C70 showed no detectable binding. This discrimination was
attributed to the relatively rigid structure of 169.3.
DN
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Scheme 170. Acenaphtho[1,2-b]benzoquinolinesa
section 5.4). Phospholes C47.10ab and several of their

derivatives were reported in 2011 by Matano and coworkers.1003 These molecules were characterized by high
electron anity, yielding stable radical anions. Thin lm of
the P-sulde of C47.10b showed a high electron mobility of 2.4
103 cm2 V1 s1 at E = 4.3 105 V cm1.
Annulations with appropriately designed nucleophiles,
performed on diones 167.1 and 167.3, can proceed via a
combination of imine and aldol-type condensations, typically
resulting in the formation of a pyridazine ring. For instance,
fusion of the 9-oxo-1,9a,10-triaza-9-hydroanthracene motif to
acenaphthylene yields C48.1 (Chart 48), a yellow dye known
Chart 48. Pyridazine[a]-Fused Acenaphthylenes and Related
Systems
a
Reagents and conditions: (a)1010 2-naphthylamine, EtOH, HCl,
reux, 45 h; (b) 1-naphthylamine, EtOH, HCl, reux, 45 h; (c)1011
alkyllithium (R = Me, n-Bu, s-Bu), THF, TMEDA, 0 C or rt, 1.51.75
h, 5082%.
(171.211017 and 171.221018), and pyrylium (171.23995)

moieties.
In 1973, Zander et al. reported the synthesis of a -expanded
phenothiazinyl radical 171.18.1019 Initially, amine 171.6 was
thermally condensed to provide di(uoranthen-3-yl)amine
171.17, accompanied by traces of the -expanded phenazine
171.16. Cyclization of 171.17 with elemental sulfur followed by
oxidation with PbO2 produced the radical species 171.18. This
stable radical, which was deep-violet in the solid state, displayed
electronic spectrum with absorptions extending beyond 600
nm.
The rst synthesis of uorantheno[3,2-b]thiophene 171.27,
involving cyclization of a uoranthene thioether, was reported
in 1969 by Shenbor and Tsaberyabyi.1020 A dierent approach,
which interestingly did not start from a uoranthene derivative,
was described in 1990 by Lee-Ru and Chung.1021 In the initial
step, the cyclobutane precursor 171.24 was assembled by a
[2+2] cycloaddition of an in situ-generated ketene. 171.24 was
then subjected to acid-catalyzed ring opening followed by
electrophilic annulation. The resulting 171.26 was dehydrogenated with DDQ to yield 171.27.
Pyrrole-fused uoranthene 172.3, later used as a precursor to
peripherally fused porphyrins1022 (Chart 56, section 7.1), was
synthesized by Lash et al. in a modied ZardBarton reaction
(Scheme 172).1023 The inadequate reactivity of the starting 3nitrouoranthene 172.1 toward isocyanoacetates was overcome
by using the strong phosphazene base 172.2 and reux
conditions. A dierently fused pyrrole 172.5 was eciently
synthesized through the RhIII-catalyzed annulation of Jin et
al.538 (cf., Scheme 103, section 4.5).
6.2.3. Hetero[d]fused Acenaphthylenes. The hexacyclic
system 171.28, reported in 1988 by Saalfrank, Schutz, et al., is a
rare example of a -expanded hetero[d]fused acenaphthylene
(Scheme 171).1024 The compound was obtained in a thermally
induced double cyclization of a uorenylidene-terminated
allene precursor.
6.2.4. Carbazole-Based and Related Systems. The 8Hindolo[3,2,1-de]phenanthridin-8-one (C49.1, Chart 49) and
8H-indolo[3,2,1-de]acridin-8-one (C49.2) ring systems are of
interest because of their structural relationship to alkaloids of
the canthine family.1025 Several syntheses of the parent C49.1
from patent literature,1004 the color of which can be tuned by

substitution of the terminally fused benzene ring and other
modications.10041007 Structurally related systems C48.2 and
C48.3 were developed by Alvarez-Builla et al.,1008,1009 and
showed enhaced binding to DNA via combination of a cationic
heterocycle with a PAH moiety. Aceanthrylene systems
C48.47 were reported by Amer and co-workers.979
A one-pot synthesis of two isomeric acenaphtho[1,2b]benzoquinolines 170.12 was reported in 1996 by Ray et
al. (Scheme 170).1010 The reaction involved acid-catalyzed
condensation of 2-chloroacenaphthylene-1-carbaldehyde with
appropriate naphthylamines. These compounds were later
shown to undergo regioselective addition of alkyl-1011 and
aryllithiums1012 (170.34). The selectivity was explained in
terms of Li coordination to the quinoline nitrogen.
6.2.2. Hetero[e]fused Acenaphthylenes. Straightforward
functionalization of the [b] edge of uoranthene (corresponding to the [e] edge of the acenaphthylene substructure), and the
availability of key derivatives, such as 171.1, 171.3, and 171.6,
provided initial access to hetero[b]fused uoranthenes. First
examples of these systems, published mostly in the 1950s, were
provided by Buu-Ho and Jacquignon976 (171.2), Kloetzel et
al.1013 (171.4), Campbell and Temple1014 (171.5), and Barret
and Buu-Ho488 (171.78). In the following decade, the BuuHo group synthesized a range of other uoranthene
derivatives, 171.9, 993 171.1013, 994 171.14, 548 and
171.15,1015 which were explored as potential carcinogens.
Shenbor and co-workers reported several further [b]fused
derivatives containing oxazole (171.19201016), imidazole
DO
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Scheme 171. Hetero[b]- and Hetero[d]fused Fluoranthenesa
Reagents and conditions: (a)1019 320 C, CO2 atmosphere, 1 h; (b)1019 (1) sulfur, 250 C, CO2 atmosphere, 10 min, (2) 1,2,4-trichlorobenzene,
PbO2, reux, 5 min; (c)1021 NEt3, DCM, 0 C to rt; (d)1021 TFA, DCM, rt, 20 min; (e)1021 PPA, 100 C, 4 min; (f)1021 DDQ, benzene, reux, 1 h.
a
and its substituted derivatives were described, starting from the

1930s work of Plant and Tomlinson,1026,1027 followed by
contributions from Teitei,1028 and Ghosh et al.1029 More recent
work from Gomez-Lor and Echavarren,1030 Bracher et al.,1031
Wiczk et al.,1032 and Xu, Yao, et al.1033 explored several
synthetic approaches to C49.1, employing dierent disconnections of the fused framework. Various aza-analogues of C49.1,
containing additional embedded nitrogens and, occasionally,
additional fused rings, were reported by Berti et al.,1034
Shipchandler and Mitscher,1035 Desarbre and Merour1036
Markgraf et al.,1037 Poupon et al.,1038 Dang and Stadlbauer,1039
Huet et al.,1040,1041 Sarragiotto et al.,1042and Bracher et
al.1031,1043 Related lactam derivatives were synthesized by
Ziegler et al. (C49.5),1044 Wolfbeis (C49.6), 1045 and
Stadlbauer et al. (C49.7).1046 Compound C49.2 was rst
reported by Eckert et al. in 1922,1047 and its chemistry was
subsequently investigated by Hayashi,1048,1049 Gilman et al.,1050
Hellwinkel and Melan,368 and Brown, Eastwood, et al.1051 Azaanalogues C49.3 and C49.4 were reported, respectively, by
Molina et al.1052 and Puzik and Bracher.1053
In 2015, Higashibayashi et al. reported the synthesis of a

doubly linked carbazole dimer 173.5 (Scheme 173).1054 This
system was made from a simple monocarbazole derivative
173.1 using three dierent routes, each including an oxidative
NN bond formation and either a reductive or an oxidative C
C coupling. When treated with triuoroacetic acid, 173.5 was
found to nonreversibly disproportionate to its radical cation
[173.5]+ and the ring-opened bicarbazole monocation [173.4H]+.
A somewhat disguised heteraacenaphthylene motif is found
in alpkinidine C50.1 (Chart 50) and similar pyrroloacridine
alkaloids, closely related to pyridoacridines discussed in sections
3.1 and 5.2. To date, two syntheses of alpkinidine analogues
have been accomplished, by Kitahara et al. in 20041055 and
Piggott et al. in 2013,1056 yielding pentacyclic systems C50.2
and C50.3, respectively. A distantly related bislactam system
C50.4 and its several substituted derivatives were obtained by
Yamaguchi et al. via multistep functionalization of enantiopure
helicenes.1057
DP
Chemical Reviews
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Scheme 172. Pyrrole-Fused Fluoranthenesa
Scheme 173. Synthesis of a Pyridazino[4,3,2-jk:5,6,1jk]dicarbazolea
a
Reagents and conditions: (a)1023 CNCH2CO2Et, 172.2 (cat.), THF,
reux, overnight; (b)538 [Cp*RhCl2]2, AgSbF6, Cu(OAc)2H2O, DCE,
110 C, 36 h.
Chart 49. Carbazole-Fused Systems
Reagents and conditions:1054 (a) N-bromosuccinimide (110 mol %),

SiO2, CH2Cl2, rt, 4 h; (b) KMnO4 (250 mol %), acetone, 60 C, 4 h;
(c) Ni(cod)2 (150 mol %), cod (150 mol %), 2,2-bipyridyl (150 mol
%), THF, 45 C, 6 h; (d) Ni(cod)2 (300 mol %), cod (300 mol %),
2,2-bipyridyl (300 mol %), THF, 80 C, 6 h; (e) FeCl3 (200 mol %),
CH2Cl2, rt, 15 min; (f) Bu4NMnO4 (200 mol %), pyridine, 70 C, 24
h; (g) TFA.
Chart 50. Benzo[cd]indol-2-ones and Related Systems
6.2.5. Carbonyl-Free Azauoranthenes. Formation of

indeno[1,2,3-kl]acridine C51.1a as a product of photorearrangement of azatriptycene was observed in 1964 by Wittig
and Steinho, who conrmed the identity of this species by an
independent synthesis (Chart 51).1058 The rearrangement was
initially proposed to proceed via a biradicaloid cleavage of a CN
bond of azatriptycene. In the 1980s, the mechanism was
investigated for C51.1ab by Iwamura et al., who demonstrated nitrene formation as an additional cleavage
route10591061 (cf., Scheme 185, section 6.4). A new synthesis
of C51.1a, involving benzyne addition to 1-aminouorenone,
was reported in 2010 by Rogness and Larock.696 Using various
annulation methods, several isomeric and expanded analogues
of C51.1a were synthesized, including C51.2,10621064 C51.3
4,1065 C51.56,468,469 and C51.7469 (for azauoranthene
systems developed by Prostakov et al., see refs 10661071).
Expanded uoranthenes containing more than one heteroatom
have also been reported, notably C51.8,1072 C51.9,859,1073,862
C51.10,862,1073 C51.11,1074 and C51.12.1075,1076 The latter
species formed in a Pd-catalyzed cyclization of the corresponding pyrazolo[3,4-b]quinoline (cf., Scheme 182, section 6.4). An
interesting species, dicarbazolylene C51.13, was described in
1950 by Plant and Tomlinson.1077 This system, which is a
carbazole cyclodimer, can also be viewed as a diaza analogue of

rubicene.
6.2.6. Miscellaneous Azaacenaphthylenes and Azauoranthenes. Several nitrogen-rich -extended acenaphthylenes have been obtained, characterized by the presence of one
or two N atoms at the junction of ve- and six-membered rings.
Such systems, which typically contain ketone or lactam
functionalities, were reported by Schefczik (C52.1, Chart
52),1078 Kappe and co-workers (C52.2,1079 C52.3,1080
C52.51081), Mohrle and Seidel (C52.4),1082 Gharagozloo et
al. (C52.6),1083 Kovtunenko et al. (C52.7),1084 and Koutentis
et al. (C52.8).1085 In contrast to C52.17, which were
DQ
Chemical Reviews
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conversion yields up to 0.42% under simulated AM 1.5 solar

irradiation.
In the systems described above, the acenaphthylene
substructure was typically expanded by ortho-fusion of additional, mostly six-membered rings. Large frameworks containing an additional peri-fusion point, for example, one embedded
in the cyclopenta[def ]phenanthrene substructure, are rarely
encountered (Scheme 174). A peri-fused pyrrole diketone
Chart 51. Carbonyl-Free Azauoranthenes
Scheme 174. Heteroaromatics Containing

Cyclopenta[def ]phenanthrene Substructuresa
synthesized by classical condensation methods, compound

C52.8 was obtained via AgI-mediated Pd-catalyzed cyclizations,
of either oxidative or nonoxidative character. Compound
C52.10, analogous to the substituent-free system C52.9
described in earlier work,1062,1086 was synthesized in 1981 by
Krepelka et al. as a potential antineoplastic agent.1087
Dyes C52.1112 were synthesized in 2011 by Wang et al.
via condensation of N-substituted quinacridones with cyanoacetic acid.1088 For each R group, a mixture of single and
double condensation products was obtained, each containing a
single ve-membered ring. C52.11 and C52.12 showed
absorption in the entire visible range, extending, respectively,
to ca. 700 and 750 nm. When employed as acceptor materials
in heterojunciton solar cells, these systems provided power
Reagents and conditions: (a)481 benzylamine, reux, 0.5 h; (b)1089

420430 C, CO2 atmosphere.
174.2 was described in 1936 by Scholl and co-workers as a

product of condensation between pentaphene-5,8,13,14tetraone 174.1 and benzylamine.481 Zander and Franke
reported the synthesis of benzo[def ]naphtho[2,3-b]carbazole
174.4, which could be obtained from each of the substituted
Chart 52. Miscellaneous Azaacenaphthylenes and Azauoranthenes
DR
Chemical Reviews
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Scheme 175. Pyracylene-Based Heterocyclesa
benzocarbazoles 174.3ab by means of the Elbs reaction

(174.3b apparently underwent deacylation).1089 Unexpected
lactamizations of dibenzophenothiazinecarboxylic acids were
observed by Shirley and Gilmer, yielding the highly fused
products 174.56.1090 This behavior was ascribed to steric
eects. Interestingly, the highly fused indazolo[4,3,2-hij]quinoline motif is found in two commercial Indanthrene
dyes, Navy Blue R (174.7) and Gray M (174.8).348 174.7 is
prepared by condensation of 3-bromobenzanthrone with
anthrapyrazole, followed by base-induced cyclization. The
synthetic proof for the structure of 174.7 was provided by
Bradley and Shah in 1959.1091
6.2.7. Pyracylene-Based Systems. The condensation of
indigo 175.1 with ethyl phenylacetate or phenylacetyl chloride
furnishes the fused 1,5-naphthyridine 175.2 known as
Cibalackrot (Ciba Lake Red B), which is an industrial dye
with photophysical properties very dierent from those of
indigo (Scheme 175).1092 The compound was described in the
1910s by Engi (see ref 1093) and subsequently by Posner and
Kemper.1094 The condensation was shown to work with other
indigo derivatives, for example, with -naphthindigo, yielding
175.3,1093 as well as with other arylacetyl derivatives. The fused
ring system of 175.2 is otherwise rarely encountered; a
structurally related molecule, 175.4, was reported in 1992 by
Somei and Kodama, as a product of double cycloaddition of
dimethyl acetylenedicarboxylate to 2,2-biindole.1095
In 2014, a bisthienyl analogue of 175.2, now renamed bayannulated indigo was used by Liu et al. as an acceptor unit for
the synthesis of donoracceptor semiconducting polymers
175.56.1096 Thin-lm OFETs fabricated with both polymers
showed ambipolar transport properties with hole and electron
mobilities reaching 1.5 and 0.41 cm2 V1 s1, respectively.
Bronstein et al. reported a similarly constructed polymer based
on the Cibalackrot core, which was successfully used as an
ambipolar OFET material.1097 In contrast to indigo, which
undergoes rapid internal conversion upon excitation, the
polymer-embedded 175.2 core was found to be an eective
photovolatic unit, providing power-conversion eciencies of up
to 2.35% in inverted BHJ devices.
Tetrakis(arylimino)pyracene 175.8, rst reported in 2008 by
Cowley and co-workers as a bifunctional ligand,1101 has been
converted to several heterocyclic derivatives. The bisimidazolium salt 175.7 obtained by Prades, Peris, and Alcarazo
by bisannulation with chloromethyl methyl ether1098 was used
as a bridging carbene ligand for Rh, Ir, and Pd.1098,1102 Cowley
et al. reported the formation of bis-phosphenium dication salt
175.9 and the bis([1,3,2]diazaborole) radical cation salt 175.10
by annulations with appropriate heteroatom sources.1099 These
two systems, and a related bis(TeI2) complex, demonstrated
dierences in electron transfer from each p-block element into
the 175.8 core, and their dependence on the character of
bonding interactions. A dierent placement of nitrogens in the
pyracylene substructure is found in diindeno[1,2,3-de:1,2,3ij]phthalazine 175.11 reported in 1989 by Bethell et al.1100 This
species, which was only partially characterized, was obtained by
thermal decomposition of 11,12-bis(diazo)-11,12-dihydroindeno[2,1-a]uorene 175.11.
6.2.8. Extended Thiaacenaphthylenes. Dithiole-fused
acenes and their Se and Te analogues, which are briey
discussed below, are an important class of organic materials
because of their remarkable conducting properties (C53.114,
Chart 53). Their chemistry, solid-state structures, and device
performance were reviewed in 2011 by Briseno and co-
Reagents and conditions: (a)1094 reux; (b)1098 MeOCH2Cl, 100 C,

20 h; (c)1099 PI3, DCM, 12 h; (d)1099 BI3, DCM, 12 h; (e)1100
mesitylene, 100 C, 3.5 h.
a
workers.28 Fused dithiole rings are commonly synthesized by

direct reactions of acenes with elemental chalcogens. Such
reactions are often unselective and require fairly high
temperatures, which are typically achieved by reuxing in
DMF or 1,2,4-trichlorobenzene. Large, multiply substituted
systems, such as the hexasulde C53.12,1103 can be obtained
using this approach. With larger molecules the solubility
becomes very low, as in the hexacene substitution product, for
which two alternative structures C53.1314 were considered.1103 Nucleophilic displacement of halogens by means of
dichalcogenides can provide certain substituted derivatives,
such as C53.1011 (for a related synthesis, see the perylene
derivative 61.9, section 3.4). Similarly, C53.7 can be
DS
Chemical Reviews
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Scheme 177. Se- and Te-Bridged Triphenylenesa
Chart 53. Edge-Fused Chalcogenoacenes
Reagents and conditions: (a)1108 Na2Se2, THF, 24 h, rt; (b) Na2Te2,

THF, 24 h, rt; (c) DDQ, PhCl, reux 10 h.
the oxidative step, and the resulting product mixtures could not
be separated without decomposition.
A dierent type of thia-containing 5-6-6 system was reported
in 1986 by Nakasuji, Murata, et al. (Scheme 178).1109 1,2Scheme 178. Pentalene-Fused Thioxanthenea
synthesized from tetrachloroanthraquinone and sodium sulde

(see refs 11041106 and earlier work cited therein).
A highly stable trithiapentaleno-fused pentacene-7-one 176.4
was reported in 2014 by Kintigh et al.1107 The compound is
deep-blue when dissolved in chloroform, with an optical
bandgap of 1.90 eV, and forms a densely stacked structure in
the solid state, stabilized by a combination of and CH
interactions. It showed activity in bilayer photovoltaic devices,
which improved considerably upon increasing the temperature.
Reagents and conditions: (a)1109 AlCl3, NaCl, 240250 C, 30 min.
Di(thioxanthen-9-ylidene)ethene 178.1 was subjected to

oxidative double cyclization under Scholl conditions, providing
a moderate yield of the dark-violet product 178.2. Despite the
low solubility in organic solvents, the rst oxidation potential of
178.2 was determined at ca. +0.72 V vs SCE. 178.2 formed
charge-transfer complexes with DDQ, TCNQF4, and TCNQ as
acceptors, characterized with a variable degree of CT character.
6.2.9. Fused Oxaacenaphthylenes. Extended 5-6-6-fused
structures containing oxygen (either in a 5- or a 6-membered
ring) are occasionally formed in rather exotic, and not
necessarily related, systems. Grinev et al. reported the
conversion of 179.1 into 179.2 via an intramolecular
FriedelCrafts acylation.1110,1111 As part of their research on
bis(alkyne) cycloaromatizations, Dom nguez et al. reported in
2004 a complex transformation of the substituted xanthenol
179.3 into the indenoxanthenone 179.4, which was crystallographically characterized.1112 The reaction was proposed to
proceed via alkyneallene rearrangement, followed by
Schmittel cyclization, radical acetylation, and aldol-type
cyclization.
When treated with perchloric acid, the extended starphene
ketone C54.1 undergoes intramolecular cyclization, to form the
extensively fused, emerald-green furan derivative C54.2a
(Chart 54). The formation of such extended furans and their
reactivity were investigated in the 1930s by Pummerer and coworkers,203,1113,1114 and subsequently by Fierz-David et al.1115
and Laatsch.1116 In particular, C54.2a can be acetylated to the
singly and doubly substituted derivatives C54.2bc, and
reductively acetylated to produce C54.3.1116 Even more
extended furans, red-violet C54.4 and orange C54.5, were
Scheme 176. Trithiapentaleno-Fused Pentacene-7-onea
Reagents and conditions: (a)1107 N2, HI/HOAc, reux, 6 h; (b) N2,

NaBH4, THF:H2O (5:1), reux, 3 h; (c) N2, DMF, S8, reux, 24 h; (d)
N2, TCB (1,2,4-trichlorobenzene), S8, reux, 4 h.
Bay-annulated triphenylenes containing Se and Te bridges

(177.3a4a and 177.3b4b) were described by Singh et al. in
2014 (Scheme 177).1108 These systems were obtained by
means of nucleophilic bridging of the saturated hexabromo
derivative 177.1, followed by oxidative aromatization/ring
contraction of the triply annulated intermediates 177.2ab.
Unfortunately, the bridges were unselectively cleaved during
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Scheme 179. Miscellaneous Oxaacenaphthylenesa
of nitro precursors such as 180.5, providing access to 180.2 and

a range of its substituted derivatives,1122,1123 and aza analogues
180.57.1124 Compound 180.2 shows strong uorescence
emission (378 nm, quantum yield 0.41).1122 180.2 undergoes
electrochemical and chemical dimerization, yielding compounds 180.810,1122 and has been shown to form conducting
lms upon oxidation.1122,1123 Liu et al. developed Heck
cyclizations of halogenated precursors (yielding, for instance,
180.6),1125 which were subsequently used to prepare materials
for dye-sensitized solar cells1126 and to synthesize a new range
of planarized donors for PHOLED applications.1127
By extending the synthetic strategies described above,
Khodorkovsky et al. succeeded in preparing dibenzo[2,3:5,6]pyrrolizino[1,7-bc]indolo[1,2,3-lm]carbazole 180.12 and a
range of its substituted derivatives. 180.12 contains a doubled
pyrrolo[3,2,1-hi]indole motif, which was assembled using either
the diazonium method (from 180.11) or the Ullmann
amination route (from 180.13).1128 The low yield of the
diazonium route resulted from its imperfect regioselectivity.
Indolocarbazole 180.13 was prepared from bis(indolyl)methane 180.141128,1129 or the dimethylbarbituric derivative
180.15.1130 180.12 is a uorescent compound, characterized by
uniquely small Stokes shifts and quantum yields close to 100%,
and shows moderate TPA cross sections (ca. 20 GM at 850
nm).
Zhang et al. reported a synthesis of benzo[c]pyrrolo[1,2,3lm]carbazoles (e.g., 180.18, Scheme 180).1131 The initial step
involved a double photocyclization of a tethered indole
styrene precursor 180.16, which was followed by the DDQmediated aromatization of the pentacyclic intermediate 180.17.
A cross-conjugated diaza system 180.21, containing the
pyrrolo[3,2,1-hi]indole substructure and three exocyclic double
bonds, was reported by Kovtunenko et al.1132
6.3.2. Fused Pyrrolo[2,1,5-cd]indolizines. The pyrrolo[2,1,5-cd]indolizine motif, isomeric with pyrrolo[3,2,1-hi]indole, constitutes the basis of a range of fused derivatives.
The most important ve-ring system, benzo[1,2]indolizino[3,4,5-ab]isoindole 181.3a, was rst reported by Matsumoto
and co-workers. 1133,1134 Pyridinium dicyanomethylides
181.1ad underwent dipolar cycloadditions with benzyne,
providing moderate yields of 181.3ad and the monocycloaddition intermediate 181.2ad (Scheme 181). Further renements of this method enabled the synthesis of other fused
systems, such as 181.3,1135 181.4,1136 and 181.5.1137 The
peculiar conjugated structure of 181.3a was the subject of some
interest. A peripheral conjugation pathway encircling the
internal nitrogen was proposed by Matsumoto et al. on the
basis of 14N NMR and redox data.1138 Wudl and co-workers
reported another cycloaddition synthesis of 181.3a, starting
from pyrido[2,1-a]isoindole 181.6.1139 The latter compound
was also used for the preparation of pyridazine-fused derivatives
181.810. The introduction of the pyridazine ring caused a
marked increase in uorescence quantum yields (82% for
181.10, 40% for 181.3a in DMSO). The observed Stokes shifts
were generally below 20 nm.
a
Reagents and conditions: (a)1110,1111 (1) SOCl2, CCl4, (2) AlCl3;
(b)1112 toluene, AcOH, 115 C.
Chart 54. peri-Fused -Extended Furans
reported in 1992 by Laatsch and co-workers.1117 The reactivity

involved in the formation of C54.25 is closely related to the
chemistry of tetrabenzotetraoxa[8]circulene 159.1 (Scheme
159, section 6.1).
6.3. Cyclopenta[cd]indene Systems
The 5-5-6 peri-fused ring system (cyclopenta[cd]indene, cf.,

Chart 43) is quite highly strained, and therefore rarely
encountered in large -conjugated frameworks. The two most
prevalent heterocyclic motifs, pyrrolo[3,2,1-hi]indoles and
pyrrolo[2,1,5-cd]indolizines, are discussed below. For a
dynamic 2a-selenacyclopenta[hi]indene system and related
molecules, see papers by Reich et al.1118,1119
6.3.1. Fused Pyrrolo[3,2,1-hi]indoles. Indolo[3,2,1-jk]carbazole 180.2 was rst reported by Dunlop and Tucker, who
performed a thermal cyclization of the diazonium salt derived
from 180.1 (Scheme 180).1120 The strained ring system in
180.2 was initially presumed to contain a pyramidal nitrogen
center, an assumption that was shown to be incorrect in
subsequent structural studies. 180.2 was later synthesized from
the anhydride 180.4 by Brown, Eastwood, et al.1051 Their
reaction, which involved pyrolytic generation of the aryne
intermediate 180.3, gave a superior yield of 83%. A related FVP
approach developed by McNab et al.1121 involved the pyrolysis
6.4. peri-Fused Seven-Membered Rings
6.4.1. peri-Fused Cycloheptatrienes. Heteroaromatic

systems in which six or more rings are peri-fused to a central
cycloheptatriene ring have been classied as [7]circulenoids
and are discussed in section 6.1. Apart from circulenoids, large
heterofused cycloheptatrienes are modestly represented in the
literature, with a notable early example provided by Fiesers
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Scheme 180. Fused Pyrrolo[3,2,1-hi]indolesa
Reagents and conditions: (a)1120 (1) NaNO2, H2SO4, H2O, (2) reux; (b)1051 900 C, 0.03 Torr; (c)1122 875 C, 0.02 Torr; (d)1125 Pd(OAc)2,
PPh3, BnEt3NCl, K2CO3, DMA, reux, 4 h; (e)1128 activated Cu, H2SO4, H2O, 9%; (f) solid, exposure to sunlight, 12%; (g) CuI, [NBu4]OH, DMF,
74%; (h)1128,1129 I2, MeCN, reux, 25%; (i)1130 AcOH, reux, ca. 40%; (j)1131 500 W medium pressure Hg lamp, acetone, pyridine, 12 h; (k), DDQ,
DCM, rt, 12 h; (l)1132 NEt3, DMF, reux; (m) p-dimethylaminobenzaldehyde, Ac2O, reux, 30 min.
a
Scheme 181. Fused Pyrrolo[2,1,5-cd]indolizinesa
a
Reagents and conditions: (a)1133 i-AmONO, anthranilic acid, DCE, DME; (b)1139 2,2,6,6-tetramethylpiperidine, n-BuLi, bromobenzene, THF, 78
C, 1 h; (c)1139 dimethyl maleate, CH2Cl2, 0 C, 1 h; (d)1139 hydrazine, EtOH, chlorobenzene, reux, 5 days; (e)1139 PCl5, POCl3, 130 C, 4 h;
(f)1139 phenol, K2CO3, DMF, reux, 3 days.
pleiadenoisoxazolones (e.g., 182.2, Scheme 182), which were

obtained in 1933 by cyclization of appropriate oximes.1140 A
fused cyclohepta[cd]benzofuran derivative 182.4 was synthesized in 2010 by Mehta and Larock, who used a potentially
highly general Pd-catalyzed alkyne annulation strategy.1141 A
versatile method of synthesizing fused 1,2,3-triazabenzo[cd]azulenes 182.61075,1076,11421144 and 182.71145 was developed
by Danel and co-workers. Their strategy involves a threecomponent assembly of substituted pyrazolo[3,4-b]quinolines
182.5, which were subsequently cyclized to 182.6, possibly via
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Scheme 182. peri-Fused Cycloheptatrienesa
a
(a)1140 acid or base; (b)1141 Pd(OAc)2, NaOAc, TBAC, DMF, 100 C, 24 h; (c)1075,1076,11421144 ethylene glycol, reux, 3 h; (d) KOH,
isoquinoline, reux, 2 h, 3070%.
Scheme 183. Synthetic Chemistry of Arcyriacyanin A and Radermachola
Reagents and conditions: (a)1150 (1) AcOH, 80 C, MW heating, 10 min, (2) t-BuOK, THF, 25 C, 1 h; (b)1147 (1) EtMgBr, THF, rt, 2 h, (2) 3,4dibromomaleimide, toluene, 110 C, 2 h; (c) Pd(OAc)2, dppp, NEt3, DMF, 110 C, 18 h; (d) Pd(OAc)2, PPh3, NEt3, MeCN, 80 C, 3 h; (e)1151 (1)
NaBH3CN, THF, 0 C, (2) 180 C, 5 min; (f)1152,1153 (1) Me3SiI, CDCl3, rt, 27 h, (2) MeOH, (3) p-TsOH, benzene, reux, 5 h; (g)1154 (1) NaH,
THF, (2) BuLi, 78 C to rt.
a
Joshi, Pelletier, et al.1152,1153 Their method relied on the closure

of the peri-fused furan ring in the nal step, a strategy that was
retained in a modied synthesis of 183.11 described by Hauser
and Yin.1154 A four-step total synthesis of radermachol,
involving nal cyclization of the 7-membered ring in 183.12,
was reported in 2014 by Buccini and Piggot.1155
6.4.2. Fused Azepines and Diazepines. An early example
of a heteroaromatic benzo[cd]azulene was provided by the
synthesis of the 184.3 dye, known as Ciba Yellow 3G, which
was obtained by heating indigo with benzoyl chloride and
copper, as rst reported in 1914 by Engi (Scheme 184).1093,1156
184.3 can also be obtained in two steps by thermal
decomposition of 184.2 (Dessoulavys compound). When
184.2 or its hydroxy analogue (184.1, Hochst Yellow R) are
heated with sulfuric acid, they are converted into Hochst
Yellow U (184.4), a dye isomeric to 184.3. The correct
structures of 184.3 and 184.4 dyes were established in 1949 by
de Diesbach and co-workers,1157 and the structure of 184.3 was
conrmed crystallographically.1158 Extensively fused azepin-4ones were also described by Niume et al. (184.5),1159
Palmisano et al. (184.6),1160 and by Chardonnens and
a benzyne intermediate. If the C-substituent on the pyrazole

ring is nonaromatic, the cyclization reaction leads to
azauoranthene products C51.12 (section 6.2). 182.6 derivatives exhibiting stable glassy states were explored as OLED
materials, emitting greenish-yellow light in ITO/PEDOT:PSS/
azulene/Ca/Al devices.1146
Two systems of particular interest, to which a considerable
synthetic eort was directed, are the natural products
arcyriacyanin A 183.4 and radermachol 183.10 (Scheme
183). Three routes to 183.4 (isolated from the slime mold
Arcyria obvelata), starting from 183.3, 183.6, or 183.7, and
based on organomagnesium or Heck-type couplings, were
reported in 1997 by Steglich et al.1147 The route involving
183.3, which was also explored by Tobinaga et al.1148 and
Murase et al.,1149 was subsequently extended by Kraus and
Guo, who synthesized the 183.3 precursor in one step, using
the 2-aminobenzyl phosphonium salt 183.1.1150 An alternative
route to 183.5, based on the nal indolization of aminonitrile
183.9, was also reported by the Steglich group.1151 The red
pigment radermachol 183.11, isolated from the bignonia plant
Radermachera xylocarpa, was rst synthesized in the 1990s by
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Gamba (184.79).1161 The latter three systems were obtained

using either imine or oxime cyclizations in the nal ringforming step.
Fused azepines 185.2 were prepared in 1972 by Hellwinkel
and Seifert, in an electrophilic cyclization of a diazonium salt
generated from 185.1.1162 Iwamura et al. reported the partly
conjugated azepine 185.10, which was obtained by photorearrangement of 1-azatriptynecene 185.61163 (cf., compound
C51.1a, section 6.2). The mechanism of this reaction begins
with the formation of nitrene 185.7, which is transformed into
azanorcaradiene 185.8. The latter species rearranges into
185.10 under basic conditions. Hydride abstraction from
185.10 produced the fully conjugated cation 185.11. A similar
type of reactivity could also be induced for nitrenes generated
by photolysis of appropriate azides.1061 In 2013, a method of
synthesizing densely substituted benzazepines (e.g., 185.4)
through Pd-catalyzed oxidative cycloadditions of acetylenes to
isatins was reported by Jiang, Wang, et al.1164 To demonstrate
the utility of such derivatives, compound 185.4 was oxidatively
coupled to the highly fused benzazepine 185.5. An unusual
tandem bis-annulation of a doubly N-confused dipyrrin
185.13 to isomeric azaheptalenes 185.14 and 185.15 was
observed by Anand and co-workers.1165
Oxidation of methylene-3,3-diindolizine 186.1 with chloranil followed by anion exchange, in 1966 reported by Reid et
al., yielded the green pentacyclic diazepine cation 186.2.1166
The cation could be cleanly reduced with sodium borohydride
in methanol to the red neutral product 186.3. Benzo[b]uoreno[1,9-ef ][1,4]diazepines 186.8 were synthesized by
Baxendale et al. using ow techniques.1167 Further examples
of related systems include carbazole-derived pentacyclic
diazepines 186.4 reported by Voelter et al.1168 and carbolinediazepines 186.5 of BeugelmansVerrier and Potier,1169 and
the hexacyclic purine 186.6 obtained by Taylor and Yoneda in a
reaction of 1,3-dimethyl-4,5-diaminouracil with anthranilic
Scheme 184. Indigo Yellow Dyes and Other Azepinone

Systemsa
Reagents and conditions:1156 (a) PhCOCl, reux; (b) PhCOCl, Cu

powder, nitrobenzene, reux; (c) heat, loss of PhCOCl; (d) conc.
H2SO4, 130 C.
Scheme 185. Azepines with Extended peri-Fusiona
Reagents and conditions: (a)1162 (1) NaNO2, AcOH, H2O, sulfamic acid, (2) heating, (3) Al2O3 chromatography; (b)1164 Pd(OAc)2, AgOAc,
MeCN/dioxane, 100 C, 24 h; (c) Cu(OTf)2, AlCl3, CS2, rt, 24 h; (d)1163 h, MeOH, MeONa; (e) [Ph3C][BF4], ether/chloroform; (f)1165 DDQ;
(g) Fe(acac)3; (h) Cu(OAc)2.
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acid.1170 A hexacyclic urea derivative 186.10 was obtained by

Lautens et al. using a new general strategy, which involves
Thiourea derivatives of 187.3 showed activity as inhibitors of

bacterial and human protein kinases.1174
6.4.3. Oxa- and Thia- 7-Membered Rings. A naphthalene-annulated oxepin 188.2, structurally related to [7]circulenes, was prepared by Konig et al.1176 The central ring
was eciently closed by acid-catalyzed intramolecular condensation of the corresponding binaphthalene precursor 188.1
(Scheme 188). Oxepin 188.2 was subjected to a sequence of
Scheme 186. Fused Diazepinesa
Scheme 188. Chemistry of Annulated Oxepinsa
a
Reagents and conditions: (a)1176 p-TsOH, toluene, reux; (b) NBS,
DMF, 40 C; (c) PhB(OH)2, K3PO4, Pd(OAc)2, P(o-Tol)3, toluene/
dioxane/water, 70 C; (d) NBS, DMF, 80 C.
brominations and Suzuki couplings (188.36), which established a straightforward route to aryl-functionalized derivatives.
Compounds 188.2, 188.4, and 188.6 are uorescent in
solution, showing emission maxima in the 427465 nm range.
As part of their 2004 study on the synthesis of fused
polycycles by 1,4-palladium migration chemistry, benzo[f ]uoreno[1,9-bc]oxepin 189.4 was synthesized by Larock and
co-workers (Scheme 189).1177 The reaction was proposed to
proceed via intramolecular migration of Pd between the
palladated intermediates 189.2 and 189.3. A route toward
benzannulated oxazepinocarbazoles 189.6, using Pd-catalyzed
intramolecular CO cross-coupling, was reported by Prasad et
al.1178 A pentacyclic dibenzoxepin lactam 189.10 was obtained
by Heo et al. using a Cu-catalyzed one-pot etherication/aldol
condensation cascade reaction.1179 Irradiation of dibenzothiophene precursors 189.11 produced, in addition to phenanthro[4,5-bcd]thiophenes, also the corresponding pentacyclic
thiepines 189.12, as reported by Furukawa et al.1180 Fused
1,4-thiazepines, such as 189.13 and its analogues containing
two 7-membered rings, were obtained by Galt et al. in reactions
Reagents and conditions: (a)1166 (1) chloranil, MeOH, (2) HClO4,

MeOH, reux; (b)1167 NaBH4, MeOH; (c)1168 (1) n-BuLi, MW
heating, (2) PtO2, ow hydrogenation, 3751%; (d)1171 186.11,
K2CO3, CsOPiv, toluene, 100 C.
domino Heck coupling of 2,2-dibromovinylarenes, catalyzed by

palladacycle 186.11.1171
Diazepine 187.3, containing the [1,4]diazepino[1,7-a:6,5,4hi]diindole framework isomeric to that found in arcyriacyanin
A (183.4), was synthesized by a cyclizationaromatization
sequence by Preobrazhenskaya et al. (Scheme 187).1172 This
strategy enabled the synthesis of substituted derivatives of
187.3,1173,1174 as well as other related ring systems, such as the
benzologue 187.41172 and the monoazepine isomer 187.5.1175
Scheme 187. Diazepinodiindolesa
Reagents and conditions:1172 (a) TFA, DCM, rt, 2 h; (b) DDQ, toluene, reux, 1 h.
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Scheme 189. 5-6-7-Fused Oxepins and Thiepinesa
Reagents and conditions: (a)1177 Pd(OAc)2, dppm, CsO2CCMe3, DMF, 110 C; (b)1178 Pd(OAc)2, Cs2CO3, TBAB, DMF, 100 C, 2 h; (c)1179
Cu, Cs2CO3, pyridine, 150 C, 24 h; (d) photochemical, benzene; (e) NaOH, dioxane/EtOH/water, reux, 30 min; (f) Cu bronze diethyl phthalate,
94% as picrate; (g)1181 PCl3, 1,2-DCE, 80 C, 12 h.
a
Chart 55. Classication of Macrocyclic Systems Used in This Sectiona
The macrocyclic fragment is shown in blue; -conjugation and positions of optional heteroatoms are not indicated.
of substituted anthraquinones with 2-aminobenzenethiol.164

Subsequent Cu-mediated extrusion of sulfur from 189.13
yielded the dibenzoacridine derivative 189.14.
A class of V-shaped acene analogues 189.16 containing a
combination of oxepin and pyrrole rings was reported in 2016
by Jursen as and co-workers.1181 These molecules were obtained
from the dicarboxylic precursors 189.15 in a single step
consisting of a double FriedelCrafts acylation and dehydrative
formation of the oxepin. Compounds 189.16 were uorescent,
with maxem at ca. 545 nm, and quantum yields in the 0.030.05
range. Hole drift mobilities of up to 8 104 cm2 V1 s1 were
measured for wet-casted lms of these materials under ambient
conditions.
7. MACROCYCLIC SYSTEMS
At rst glance, macrocyclic systems may seem quite distinct
from other polycyclic heteroaromatics. However, extensively
fused macrocycles can be viewed as punctured nanographenes, and bear structural relationships to many classes
of PHAs discussed above. At the same time, macrocyclic
systems are distinguished by the unique repertoire of methods
used to synthesize them. They additionally exhibit extraordinary reactivity patterns, and unusual electronic features. In line
with the scope of this Review, our principal focus is on systems
that are peri-fused and contiguously -conjugated, although not
necessarily planar. Acetylene-based macrocycles are excluded,
except for shape-persistent, planar molecules.
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Scheme 190. Syntheses of Acenaphthoporphyrinsa
Reagents and conditions:1201 (a) (1) ethyl isocyanoacetate, DBU, THF, rt, 16 h; (2) KOH, ethylene glycol, reux; (b) 7% AcOHEtOH, N2,
reux, 16 h; (c) (1) TFA, N2, 10 min, (2) CH2Cl2, N2, 25 C, 2 h, (3) Et3N, 1 equiv of DDQ, 1 h.
systems have been included in the preceding sections, but the

majority is grouped here for consistency. With the exception of
section 7.1, all macrocycles presented in this chapter are ortho-,
peri-, and macro-fused, as dened in the Introduction (section
1.2). This type of fusion can be achieved in porphyrinoids by
condensing an aromatic ring to adjacent meso and positions
(sections 7.2, 7.3, and 7.4), by incorporating a polycyclic
subunit in the macrocycle (section 7.5), or by introducing
internal bridges into an existing structure (section 7.6).
Polycyclic building blocks are typically assembled prior to the
synthesis of the macrocycle, which is designed to span more
than one ring of the subunit.
A catch-all taxon peri-fused cyclophanes is created for the
remaining systems, which are discussed in section 7.7. Many of
the relevant cyclophane families contain members with highly
variable geometries, ranging from planar, through rued, to
highly distorted, which makes the selection process quite
dicult. Thus, even though our principal focus is on planar,
well-conjugated molecules, some very contorted cyclophanes
are also included for consistency.
Macrocyclic aromaticity is an important feature of many
systems discussed below. Where necessary, we indicate
conjugation circuits with bold bonds, especially in sections
dealing with porphyrin analogues (for a more detailed
discussion of -conjugation in porphyrinoids, see refs 1193
and 1182). As in preceding sections, bold bonds are also used
In the current literature, heteroaromatic macrocycles

containing peri-fusion points, which are the subject of the
following sections, are typically classied as either porphyrinoids or (hetera)cyclophanes. The term porphyrinoid has no
precise denition and currently encompasses a large group of
porphyrin-like macrocycles, including some hydrocarbon
systems.1182 Formally, all porphyrinoids meet the current
IUPAC denition of cyclophane,1183 but it is nevertheless
convenient to retain the former term for practical reasons. In
the following discussion, the structures will generally be
classied as porphyrinoids if they were considered as such by
the original authors. Various aspects of porphyrinoid chemistry,
relevant to the present chapter, have been reviewed by several
groups.1182,11841190 A few more general reviews on heteroaromatic macrocycles have also been published, notably the
yearly chapters in Progress in Heterocyclic Chemistry by
Newkome (since 1989)1191 and a chapter on heteracyclophanes
by Vogtle et al.1192 The largest circulene systems, which
constitute a small class of macrocycles dierent from both
porphyrinoids and cyclophanes, have been reviewed in section
6.1.
The material is classied according to the topological features
of the macrocycle and underlying synthetic chemistry (Chart
55). In section 7.1, we discuss molecules containing an orthoand peri-fused ring system that is itself ortho-fused to a pyrrolic
bond of a porphyrinoid macrocycle. A few of those
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Chart 56. [b]-Fused Porphyrins Containing Fluoranthene, Pyrene, Corannulene, and Dibenzo[fg,op]tetracene Subunits
Scheme 191. Synthesis of Acenaphthylene-Fused Cyclo[8]pyrrolesa
Reagents and conditions:1212 (a) CNCH2CO2Et, t-BuOK; (b) (1) benzyltrimethylammonium dichloroiodate (BTMSICl2), CaCO3, CH2Cl2,
MeOH, (2) (Boc)2O, 4-dimethylaminopyridine (DMAP), CH2Cl2; (c) (1) Cu powder, DMF, 110 C, (2) conc. HCl, AcOEt; (d) NaOH,
(CH2OH)2, 170 C; (e) Ce(SO4)2, conc. H2SO4, Na2SO4, N(n-Bu)4HSO4, CHCl3, reux, 27 h.
method 1.1197,1198 [b]-Fusion has been extensively applied as a

method of expanding the -conjugated system of the porphyrin,
and the eld was reviewed by several authors.1199,1200 Here, we
focus on systems containing peri-fused subunits on the
periphery of the macrocycle.
In 1996, Lash and Chandrasekar reported the rst examples
of porphyrins containing -fused acenaphthylene units.1201
The requisite monopyrrole 190.2 was obtained in moderate
yield from 1-nitroacenaphthylene 190.1, by using the Zard
Barton method (Scheme 190). Fused porphyrins 190.68 were
then synthesized in two steps using tripyrrane intermediates
190.4ac. The UVvis spectra of compounds 190.6ac
showed large bathochromic shifts relative to octaalkylporphyrins, larger than in the related naphtho-, phenanthro-, and
phenanthrolino-fused derivatives. In subsequent work, the
groups of Lash1202 and Ono1203 presented the syntheses of
tetraacenaphthoporphyrins 190.910, characterized by even
larger red shifts. For instance, in 0.5% TFAchloroform, the
to indicate out-of-plane orientation of aromatic subunits. These

two drawing conventions are nevertheless easily discerned.
7.1. [b]-Fused (-Fused) Porphyrinoids
The synthesis of [b]annulated porphyrins is typically achieved

using one of the following approaches:1194 (1) condensation of
fully conjugated [c]fused monopyrroles, (2) condensation of
nonconjugated [c]fused monopyrroles followed by aromatization of peripheral rings, and (3) condensation of -aryl
monopyrroles followed by coupling of -substituents. In
method 1, the starting monopyrroles can have a varying degree
of isoindole character, aecting their reactivity, a problem that
is not present in methods 2 and 3. In all cases, the monopyrrole
precursors are conveniently prepared by means of the Zard
Barton nitroalkeneisocyanoacetate condensation1195,1196 and
analogous reactions. In particular, nitroaromatics that have a
certain degree of nitroalkene character are able to condense
under similar conditions, providing precursors for use in
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Scheme 192. [b]-Condensed Porphyrins Containing Remote peri-Fusion Pointsa
Reagents and conditions: (a)1214 270 C, reduced pressure, 3 h, quantitative; (b)1217 Pd(OAc)2, PPh3, K2CO3, DMF, xylene, reux, 60 h; (c)1217
veratrole, FeCl3 in MeNO2, CH2Cl2, rt.
a
dication 190.9-H22+ showed a Soret band at 565 nm and several

Q absorptions at longer wavelengths (up to over 750 nm). By
varying meso substituents and metal ions, it was possible to
increase the red shift even further, and a Soret band at 642 nm
was recorded for the ethynyl-substituted lead(II) complex
190.14.1204 Apparently for steric reasons, a corrole analogue of
190.9 (R = Mes) was obtained instead of the porphyrin when
mesitaldehyde was used in the condensation.1204 Further
systems developed by Lash and co-workers include adjdiacenaphthoporphyrins 190.11ab,1205 and analogues containing six-membered rings 190.1213.1206
Kobayashi and Stillman investigated magnetic circular
dichroism (MCD) spectra of tetraphenyltetraacenaphthoporphyrin complexes with zinc1207 and other metals,1208 revealing
the eect of the saddle distortion of the chromophore on the
electronic structure of these systems. Because of their
bathochromically shifted spectra, acenaphtho-fused porphyrinoids are of interest in various applications, for example, as
sensitizers in photodynamic therapy1209,1210 and as dyes for
organic solar cells (190.15).1211 The combination of the Zard
Barton pyrrole synthesis with stepwise porphyrin macrocyclizations enabled the synthesis of further -fused
porphyrins containing uoranthene1022 (56.13), pyrene625
(56.47), and corannulene subunits912 (56.89, Chart 56), all
characterized by red-shifted optical spectra. The syntheses of
the respective monopyrroles are discussed in preceding
sections.
Acenaphthylene-fused cyclo[8]pyrrole 191.6 was described
in 2013 by Kobayashi, Okujima, et al.1212 This expanded
macrocycle was synthesized by using an oxidative coupling
reaction of the corresponding 2,2-bipyrrole 191.5, which is a
strategy typically employed for the synthesis of cyclopyrroles1213 (Scheme 191). The bipyrrole precursor 191.5
was prepared by using a BartonZard reaction of compound

191.1, followed by iodination and Boc protection of the NH
moiety. Next, Ullmann coupling of monopyrrole 191.3 was
performed, and the de-esterication of the resulting 191.4
yielded 191.5. In the synthesis of 191.6, dierent macrocyclization conditions were tested, and the best yield were
observed when utilizing Ce(SO4)2 as the oxidant in the
presence of concentrated H2SO4, Na2SO4, and N(nBu)4HSO4
in reuxing chloroform. Two conformational isomers 191.6a
and 191.6b were isolated. The less polar and lower-symmetry
isomer 191.6b could be converted into the 191.6a isomer
through a thermally induced ip of one of the constituent
pyrroles. 191.6 showed a markedly red-shifted electronic
spectrum, with the lowest energy band at 1482 nm. Application
of Michls perimeter model to magnetic circular dichroism
spectroscopic data and TD-DFT calculations demonstrated a
marked intensication of the L bands in the near-IR region
relative to a benzo-fused cyclopyrrole analogue, due to
signicant stabilization of the LUMO level in the acenaphthylene-fused 191.6.
Benzo[k]uoranthenoporphyrin 192.2, reported in 2006 by
Okujima, Ono, et al.,1214 is an example of a system with a
remotely condensed peri-fused element (Scheme 192). The
synthesis of 192.2, employing a retro-DielsAlder reaction
performed on the bicyclo[2.2.2]octadiene precursor 192.1, was
later rened by the same group, to provide the quadruply fused
derivative 192.3.1215 192.3 had the Soret band at 480 nm and a
very intense low-energy Q-band at 739 nm. The compound had
a measurable uorescence above 750 nm (F = 0.08). An even
more extended assembly of rings is found in porphyrincontaining dihydrofulvalene pincers, such as 192.4, developed
in 2006 by Johnston and co-workers.1216 192.4 consists of a
planar aromatic part (blue, Scheme 192), which is linked to the
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Scheme 193. Perylenophthalocyaninesa
phenanthroline unit (red) via a polycyclic linker (black). The

linker introduces a sharp bend into the molecule, leading to an
interplanar angle between the porphyrin and phenanthroline
parts of ca. 95, according to an AM1 calculation.
A dierent type of remotely fused system, the dibenzo[fg,op]tetracenoporphyrin 192.8, was synthesized by Wang and
co-workers.1217 Their approach was based on a tandem Heck
coupling/electrocyclization/aromatization reaction,1218 which
provided the benzo-fused porphyrin 192.6. The dibenzo[fg,op]tetracene ring system of 192.8 was then elaborated in a single
step, which involved an oxidative cyclization of the two 3,4dimethoxyphenyl substituents, followed by intermolecular
coupling with a veratrole molecule. 192.8 showed a Soret
band at 457 nm and red-shifted Q bands with increased
intensity. DFT calculations indicated that the dibenzo[fg,op]tetracene system in 192.8 is not completely planar, because of
the steric congestion caused by the OMe groups.
[b]Fused phthalocyanines were reported by several groups.
Their preparation relies on the availability of appropriate
dinitrile precursors, which are usually synthesized through
multistep routes. A notable example of a giant p-HBC-fused
phthalocyanine, reported in 2007 by the Mullen group,127 is
discussed in section 2.5 (Scheme 28). Perylenophthalocyanines
193.2ab, containing four perylene subunits bay-fused to the
phthalocyanine benzene rings, were reported in 2006 by
Cammidge and Gopee (Scheme 193).1219 These macrocycles
were obtained by Zn-templated macrocyclization of the
corresponding dinitriles 193.1ab. The syntheses were lowyielding, and because of the low solubility, the phthalocyanine
products were dicult to purify and characterize. Both
derivatives were non-mesomorphic, with melting points above
300 C. As a consequence of peripheral pyrene fusion, the
electronic spectrum of 193.2a was strongly red-shifted, relative
to the corresponding phthalocyanine, with the lowest-energy
band at 797 nm. A phthalocyanine analogue of 193.2a,
containing one fused perylene subunit, was prepared in a 5%
yield using a mixed nitrile cyclization.
In 2011, Shimizu, Kobayashi, et al. reported the synthesis of a
boron subphthalocyanine 193.5b containing a single fused
pyrene unit (a phenanthrene unit relative to the subpthalocyanine skeleton).1220 The compound was obtained in a 0.9% yield
in a mixed condensation between the pyrene tetranitrile 193.3
and tetrauorophthalonitrile 193.4, followed by ligand
exchange. The new phthalocyanine showed moderately strong
uorescence (F = 0.07) with the maximum intensity at 601
nm and a Stokes shift of 224 cm1. Pure 193.5b formed stacked dimers in the solid state, whereas in cocrystals with C60,
it was observed to produce a 2:1 complex, with two
subpthalocyanines embracing one fullerene molecule.
Several derivatives of 4,5-pyrenocyanine 193.7ae, containing dierent peripheral substituents and metal centers, were
prepared in 2012 by Mullen et al.1221 Their synthetic method
resembled that used by Cammidge et al., but the isolated yields
were considerably higher in Mullens work. The position of the
lowest energy Q-band was dependent on the metal center
(reaching 727 nm for 193.7d), and the absorption spectra
showed considerable temperature dependence in toluene
solutions. Self-assembly of pyrenocyanines was examined at
the liquid/HOPG interface as well as in the bulk, showing
features consistent with the disc-like shape of the molecules. A
number of crystalline and LC phases were observed for
193.7ae, characterized by hexagonal and rectangular packing
symmetries and varying degrees of molecular tilt.
Reagents and conditions:1219 (a) hexanol, DBU, Zn(OAc)2; (b)1220

BCl3, 1-chloronaphthalene, 230 C; (c)1220 phenol, 0.9% over two
steps; (d)1221 MCl2 (except for 193.7b), DBU, 1-pentanol, reux,
overnight.
7.2. Benzo[cd]-Fused Porphyrinoids
7.2.1. Benzo[cd]-Fusion via meso-Substituent Coupling. Coupling of a polycyclic meso-substituent to an adjacent

-pyrrolic position is one of the simplest general methods of
constructing benzo[cd]fused porphyrinoids. The scope of the
reaction is easily extended to encompass naphtho[2,1,8,7-bcde]fused systems, discussed in the following section.
An initial example of -fusion involving a nonporphyrinic
substituent was reported in 2005 by Cammidge and co-workers
(Scheme 194).1222 Compound 194.3 was obtained as an
intramolecular Heck-type side product in the attempted Suzuki
reaction between porphyrin triate 194.1 and ferrocene
bis(boronic acid) 194.2 in 14% yield. Surprisingly, only trace
quantities of 194.3 were observed when the reaction was
performed under identical conditions in the absence of 194.2.
An oxidative variant of such a fusion was described in 2007 by
Imahori et al., who synthesized naphthalene-fused zinc
porphyrin carboxylic acid 194.7 via oxidative dehydrogenation
of the meso-naphthyl precursor 194.4.1223 In comparison to the
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Scheme 194. Intramolecular Benzo[cd]-fusion via meso-Substituent Couplinga
Reagents and conditions: (a)1222 PdCl2(dppf), Ba(OH)2, DME, H2O, reux, 3 days; (b)1223 (1) FeCl3, CH2Cl2, CH3NO2, rt, 30 min, (2) TFA,
H2SO4; (c)1223 (1) KOH, H2O, THF, EtOH, reux, 4 h, (2) Zn(OAc)2, CHCl3, rt, 4 h; (d)1224 Fe(ClO4)3, MeNO2, DCM, 20 C; (e)1234
Fe(ClO4)32H2O, MeNO2, CH2Cl2.
only with meso substituents but also with activated -aryl

groups.1194,1231 Its eciency is however controlled by structural
and electronic factors. Attempts to fuse nonactivated benzenoid
PAH substituents are generally ineective, although a pyrene
bisporphyrin hybrid 248.5a1232 and bis-perylene porphyrins
anti-198.5 and syn-198.51233 were successfully prepared by
FeCl3 oxidation of the corresponding hexaarylbisporphyrin and
tetraarylporphyrin (Scheme 248, section 7.3, and Scheme 198).
The latter result was explained in terms of the low oxidation
potential of the perylene moiety (0.61 V vs Fc+/Fc).1233
Eective coupling was also achieved with an indole-substituted
porphyrin 194.10 by Gryko and Lewtak, who obtained the
heterofused system 194.11 by oxidation with Fe(ClO4)3
2H2O.1234
Dye-sensitized TiO2 solar cells based on 194.7 and 194.12,
each obtained using the oxidative coupling route, showed
power conversion eciencies () of 4.1% and 1.1%,
respectively, under standard AM 1.5 conditions, which were
improved by 50% relative to a nonfused porphyrin reference
cell.1235 To further improve the cell performance, 5-(4carboxylphenyl)-10,15,20-tris(2,4,6-trimethylphenyl)porphyrinatozinc(II), possessing dierent light-harvesting properties, was
coadsorbed with fused 194.7 onto an TiO2 electrode. The
cosensitized cell exhibited an improved power conversion
eciency of 5.0%.
Nonbenzenoid PAHs provide an attractive class of oxidationsusceptible peripheral substituents. A family of azulene-fused
porphyrins 195.24 was synthesized by Osuka and co-workers
from the respective azulenyl precursors using an analogous
oxidative coupling strategy (Scheme 195).1236 Attempted
oxidations of the monoazulenyl derivative 195.1 with AgPF6
did not cause any conversion, whereas the use of a stronger
oxidant, DDQ/Sc(OTf)3, gave rise to a complicated product
mixture. It was found that the treatment of 195.1 with FeCl3
nonfused 194.5, the UVvisible absorption spectrum of 194.7

was red-shifted and broadened (max = 482 and 682 nm for
194.7, and 422 and 551 nm for 194.5, for the Soret and most
red-shifted Q-band, respectively). A dye-sensitized TiO2 solar
cell based on 194.7 exhibited a power conversion eciency of
4.1%, which was improved by 50% relative to the reference cell
containing the nonfused 194.5.
Oxidative aromatic coupling of porphyrins containing a
naphthyl substituent at a meso position was examined by Gryko
et al.1224 Unwanted halogenation of electron-rich precursors on
attempted oxidation with FeCl3 had been observed before by
Osuka1225 and Anderson.12261228 To avoid chlorination of
naphthyl porphyrins 194.8, various oxidative systems were
tested. Utilizing oxidants such as PIFA/BF3Et2O, DDQ/
Sc(OTf)3, Mn(CH3COO)3, and Fe(OTf)3 led to the formation
of the desired product in poor yields, while reactions with other
transition metal salts (CuCl2,O2/[iPrMgClLiCl+TMP], Fe(acac)3, K3[Fe(CN)6], Cu(ClO4)2, molybdenum 2-etylhexanoate) proved to be absolutely ineective. Finally, it was found
that treatment of precursor 194.8 with Fe(ClO4)3 gave the extended porphyrins 194.9 with improved yields, and additionally no chlorinated byproducts were observed. The
absorption spectrum of the free-base analogue 194.9e
possessed ve well-resolved peaks with the lowest energy Qband extending up to 750 nm. 194.9e displayed uorescence in
the near-infrared region (max = 710 and 760 nm, fl = 10%).
Electrosynthetic preparation of related fused derivatives was
demonstrated by Gryko, Kadish, et al.1229,1230 The electrochemical coupling could be used to directly obtain fused
products in the dicationic form. In this manner, even
porphyrins with relatively high oxidation potentials were
successfully coupled to produce the targeted fusion pattern.
Oxidative coupling of substituents is a general method of
extending peripheral conjugation in porphyrins and works not
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Scheme 195. Synthesis of Azulene-Fused Porphyrinsa
tigated using DFT methods as a potential panchromatic organic

chromophore.1238
In 2014, Osuka, Tanaka, et al. reported that the FeCl3mediated oxidative fusion of -linked dyads 196.1ab provided
systems 196.2ab, in which the porphyrin ring and dibenzo[a,g]corannulene unit are fused to a common six-membered
ring (Scheme 196).1239 The oxidation of 196.3ab, containing
Scheme 196. Synthesis of meso- Dibenzo[a,g]corannuleneFused Porphyrinsa
Reagents and conditions:1236 (a) FeCl3, MeNO2, CH2Cl2.
under ambient conditions aorded the fused 195.2 in good

yield. Double and 4-fold ring-closing reactions, yielding
respectively 195.3 and 195.4, were achieved under similar
conditions. Curiously, the syn regioisomer of 195.3 was not
detected at all. The absorption spectra of azulenyl precursors
exhibited slightly broadened Soret and Q bands, with small red
shifts correlated with the number of azulenyl substituents (422,
426, and 437 nm for the Soret bands in 195.1, and the di- and
tetraazulenylporphyrins, respectively). The azulene fusion
makes a prominent impact on the Q bands, which are
broadened and exhibit large bathochromic shifts (1000 nm
for 195.2, 1014 nm for 195.3, and 1136 with shoulder up to
1200 nm for 195.4). The TPA cross-section values were
measured by an open-aperture Z-scan method, and the
maximum values (2) were 2050 GM at 1200 nm for 195.3,
and 7170 GM at 1380 nm for 195.4. The electronic structure of
azulene-fused porphyrins was examined by means of magnetic
circular dichroism (MCD), electronic absorption spectroscopy,
and time-dependent density functional theory (TD-DFT).1237
The MCD data suggested that the LUMO value was only
slightly larger than HOMO, in the case of porphyrin 195.2,
while in the case of the diazulene-fused 195.3, HOMO <
LUMO (where the HOMO is the magnitude of the energy
gap between the HOMO and the HOMO1 and LUMO is
the magnitude of the energy gap between the LUMO and
LUMO+1). The presence of a pseudo-A Faraday term in the
Q 00 band region of 195.4 demonstrated that the associated
excited states were accidentally near degenerate. As compared
to 195.2 and 195.3, the HOMO was destabilized because of the
antibonding interaction between the porphyrin and azulene
moieties, while the HOMO1 and the LUMO were stabilized
due to a bonding-type interaction. As a result, the Q-band of
195.4 was intensied and shifted to longer wavelengths. The
tetraazulene core present in 195.4 was subsequently inves-
Reagents and conditions:1239 (a) FeCl3, CH2Cl2/MeNO2, rt, 10 min.
a corannulenyl substituent at a -position, produced isomeric

products 196.4ab, containing ve-membered-ring junctions.
The use of DDQSc(OTf)3 as the oxidant gave inferior results.
The fused Zn-complex 196.2a displayed a Soret band at 494
nm and Q-bands at 669 and 691 nm, and showed uorescence
emission at 732 nm with an enhanced quantum yield (F =
0.049). Dyad 196.2b exhibited a similar absorption spectrum,
with no observable uorescence. 196.4a was also nonuorescent, with NIR absorptions tailing up to around 1050
nm. That optical signature was thought to reect the
contribution of the pseudo-20 electronic circuit of dehydropurpurin. The electrochemical HOMOLUMO gaps of
196.2a and 196.4a were 1.69 and 1.50 eV, respectively. The
smaller gap determined for 196.4a was rationalized in terms of
a partially antiaromatic character of this system.
Perylene anhydride-fused porphyrins 197.4 and 197.5 were
synthesized by Wu et al.1240 (Scheme 197, for related systems
containing NAP units,264 see section 3.2). The synthesis of
197.4 commenced with the preparation of the precursor 197.1,
utilizing Suzuki coupling of porphyrin boronic ester and Brsubstituted perylene monoimide. In the key step, the sixmembered ring formation was promoted by FeCl3-mediated
oxidative coupling. Preparation of 4-(dimethylamino)EF
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Scheme 197. Preparation of Perylene Anhydride-Fused Porphyrinsa
Reagents and conditions: (a)1240 FeCl3, MeNO2, CH2Cl2, rt; (b)1240 (1) KOH, t-BuOH, reux, (2) HOAc, 40 C; (c)1241 FeCl3, CH2Cl2, MeNO2,
reux.
Scheme 198. Fused Porphyrins via Thermal Cyclodehydrogenationa
Reagents and conditions: (a)1233 530 C, N2 atmosphere, preheated furnace 12 min. Redox potentials of substituent PAHs (in V) are given relative
to Fc+/Fc.
a
further red shift of the last Q-band (897 nm) relative to 197.2
(803 nm).
A high-temperature cyclodehydrogenation, obviating the
need for chemical oxidants, was used by Thompson and coworkers for the preparation of a bis-naphthalene-fused
porphyrin (Scheme 198).1233 This alternative coupling method
was particularly eective for low-potential PAH substituents
that could not be chemically coupled. Compound anti-198.2
and its syn isomer syn-198.3 were obtained in a total 7% yield
from the porphyrin 198.1 bearing unsubstituted naphthyl
phenylethynyl-substituted compound 197.5 employed a similar

synthetic route, which included a SonogashiraHagihara
coupling step needed to install the meso-alkynyl substituent.
When used in dye-sensitized solar cells, both compounds
showed broad incident monochromatic photon-to-current
conversion eciency spectra covering the entire visible spectral
range and part of the NIR region up to 1000 nm. Interestingly,
oxidation of 197.1 under more forceful conditions yielded a
mixture of 197.2 and the doubly annulated product 197.3.1241
The more extended conjugation in the latter species caused a
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Scheme 199. Annulation of 2,3-Dialkynylporphyrinsa
Reagents and conditions: (a)1245 5% cyclohexadiene in chlorobenzene, 190 C; (b)1251 PtCl2, toluene, 115 C; (c)1252 PtCl2, toluene, 90 C, 8 h;
(d)1252 toluene, 115 C, 1.5 h.
a
Scheme 200. meso-Substituent Fusion in -Extended Porphyrinsa
Reagents and conditions: (a)1253 1,4-naphthoquinone, toluene, reux, 36 h; (b)1253 10% TFA/CHCl3; (c)1255 NaI, 1,2,4-trichlorobenzene, 214 C,
7 h.
pyrenyl- (198.6, max = 815 nm), and perylenyl-annulated

derivatives (198.5, max = 900 nm). Pyrenyl-fused porphyrins
exhibited strong uorescence in the NIR spectral region, with a
progressive improvement of quantum yields (up to 13% with
max = 829 nm) with increasing degree of fusion. Analogous
porphyrins containing a single fused pyrene substituent were
groups. A range of pyrene-, perylene-, and coronene-substituted

porphyrins were successfully fused under similar conditions,
providing synthetically acceptable yields (>30%). The
absorption spectra of bis-fused porphyrins revealed a
progressive bathochromic shift in the series: naphthyl(198.2, max = 730 nm), coronenyl- (198.4, max = 780 nm),
EH
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Scheme 201. Synthesis of Quinolino-Annulated Porphyrinsa
Reagents and conditions: (a)1256 trichloroacetic acid, 175 C, 2 min.
peri-Fusion in 200.4 leads to a small bathochromic shift of

Soret and Q bands relative to the ortho-fused analogue 200.2. A
similar type of reactivity was observed in a DielsAlder
cycloaddition reaction between meso-tetraarylporphyrins and a
pyrazine o-quinodimethane derivative 200.5.1255 The latter
species was generated in situ from the corresponding 2,3bis(bromomethyl)pyrazine derivative. In the reaction with
porphyrins 200.6ac, a mixture of four product types, 200.7
10, was observed, including the peri-condensed systems
200.8ac and 200.10ac.
Mesoporphyrin dimethyl ester was used by Lugtenburg as a
starting material for the synthesis of peri-condensed quinoline
porphyrin hybrids (Scheme 201).1256 After conversion to its
nickel complex, the porphyrin was formylated via the Vilsmeier
method. Four monoformyl isomers were formed as a mixture
and subsequently converted into the corresponding acrylonitriles 201.1ad under WadsworthEmmons conditions. In the
key step, pure isomer 201.1a was treated with hot trichloroacetic acid to form the corresponding 201.2a. The same
reaction performed on a mixture of 201.1b and 201.1d
produced quinoline-fused systems 201.2a, 201.2d, and 201.2d.
A -Me group adjacent to the acrylonitrile substituent is
required for eective annulation, and, consequently, no
cyclization product was obtained for 201.1c. The quantum
yield of 0.77 was determined for singlet oxygen generation by
201.2a, corresponding to an improved eciency relative to
meso-tetraphenylporphyrin. Additionally, biological eects of
201.2a were tested, and lack of toxicity toward Chinese
hamster ovary cell was established, indicating a potential use of
this compound as a sensitizer in far-red phototherapy.
The (2-formylvinyl)-substituted porphyrin 202.1, obtained
by Boyle and Dolphin by reacting 5,15-diphenylporphyrin with
N,N-dimethylaminoacroleinphosphorus oxychloride, was
found to produce two products in a Lewis acid-catalyzed
cyclization reaction (Scheme 202).1257 The oxobenzochlorin
product 202.3 showed a long-wavelength absorption at 730 nm
and yielded an unstable carbinol 202.4 when reduced with
NaBH4. The other cyclization product formed via the
cyclization of the adjacent meso-phenyl substituent to the
obtained via chemical cyclodehydrogenation in earlier work by

Sugiura, Yamashita, et al.1242
peri-Condensation can also be achieved by coupling a mesoaryl substituent with an isoindole fragment in [b]benzoporphyrin derivatives. In 2001, Bergman cyclization1243,1244 of -dialkynyl-meso-tetraarylporphyrins 199.1ad
was investigated by Smith et al. as a route to fused porphyrin
derivatives.1245 Reuxing 199.1bd in a chlorobenzene
solution containing 5% 1,4-cyclohexadiene (CHD) gave
picenoporphyrins 199.2bd in moderate to very good yields
(Scheme 199). The absence of CHD, which acted as an
intermediate hydrogen donor, favored intermolecular reactions,
leading to a complex mixture of oligoporphyrins. Alternative
conditions, involving simple room-temperature oxidation with
DDQ, were subsequently proposed by Zaleski and coworkers.1246,1247 The Bergman cyclization was studied by the
same group at higher temperatures (up to 210 C)1248,1249 and
utilizing photochemical conditions.1250 Thermolysis of 2,3dialkynylporphyrins in the presence of a stoichiometric or even
catalytic amount of PtCl2 yielded phenanthroporphyrins 199.3
accompanied by only small amounts of the corresponding
picenoporphyrins or other side products.1251 The PtCl2mediated pathway enabled subsequent synthesis of nickel(II)
bisphenanthroporphyrins 199.7 and 199.8 and picenophenanthroporphyrin 199.4.1252 The electronic absorption spectra of
these compounds display a stepwise red shift of both Soret and
Q-bands correlated with the increasing delocalization. The
low energetic Q-band of porphyrin 199.5 was shifted
bathochromically by 35 nm from the tetraalkynyl starting
material 199.6 (max = 609 and 635 nm, for 199.6 and 199.5,
respectively). These shifts were increasingly larger for 199.7
(max = 683 nm) and 199.4 (max = 717 nm).
Cavaleiro and co-workers reported using the DielsAlder
reaction to synthesize porphyrinquinone derivatives with an
extended -system (Scheme 200).1253 2-Vinylporphyrin 200.1
was reacted with 5 equiv of 1,4-naphthoquinone to give three
dierent products 200.24. The peri-fused product 200.4
could be obtained by treating 200.3 with 10% triuoroacetic
acid in CHCl3, and subjected to further functionalization.1254
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spectrum of 203.2, the Soret-like band was observed at 520 nm

and the longest max in the Q-band region occurred at 765 nm.
Cyclic voltammograms of complex 203.2 exhibited a single
one-electron oxidation wave and two reversible one-electron
reduction waves. The electrochemical band gap of 203.2 was
approximately 1.67 eV, considerably smaller than those of
nonfused NCP rhenium complexes (1.751.97 eV).
7.2.3. Pyrido[cd]fused Systems. Pyridine annulations in
the [cd] region of porphyrin are typically achieved using mesoor -amino-substituted precursors. Unexpected formation of
condensed chlorins C57.13 (Chart 57), with incomplete -
Scheme 202. Synthesis of 5,15-Diphenyl-7oxobenzochlorin1257a
Chart 57. Pyrido-Fused Chlorins1259
Reagents and conditions: (a) BF3Et2O; (b) NaBH4; (c) air.
activated -pyrrolic position, and was shown to contain two

fused ve-membered rings sharing a tetravalent carbon.
7.2.2. Other Benzannulations. Unusual rhenium-mediated reactions of N-confused porphyrin (NCP) with 2-methyl
azaarenes, yielding peripherally -extended NCP derivatives,
were developed by Furuta and co-workers (Scheme 203).1258
By heating 203.1 with Re(CO)5Br in the presence of 2,6lutidine, a rhenium(V) complex 203.2 was obtained in 49%
yield. Compound 203.2 was also synthesized from 203.3 in an
improved 75% yield under similar conditions. The peripheral
ring fusion of 203.3 was examined with a variety of methyl
arene reactants. In the proposed reaction mechanism, the
involvement of pyridine-bound rhenium was implied in the
activation of the ortho methyl group. The rhenium-mediated
enlargement of NCP system was also observed in the reaction
with the dimethyl derivative 203.4, in which it led to the
formation of an intramacrocyclic rhenium bound methine
bridge (203.6, cf., Scheme 276, section 7.6). In the absorption
conjugation around the porphyrinic peri-fusion point, was

observed by Gold et al. in the course of metalation and
demetalation reactions of corresponding meso-N-arylamino and
meso-N-arylacetamidoporphyrins.1259 The resulting fusion
patterns lead to intensity enhancement and red shifts of
lowest-energy Q bands, which were observed in the 686725
nm range.
In 2009, Ruppert et al. reported the synthesis of the extended metalloporphyrin 204.2 via the Cadogan reaction
(Scheme 204).1260 Subsequent VilsmeierHaack formylation,
followed by FriedelCrafts cyclization, produced the bis-fused
Scheme 203. Synthesis of Rhenium Complexes of Peripherally Fused -Extended N-Confused Porphyrinsa
Reagent and conditions:1258 (a) Re2(CO)10 or Re(CO)5Br, K2CO3; (b) Re(CO)5Br, RMe; (c) Re(CO)5Br, K2CO3; (d) Re(CO)5Br, 2,6-lutidine.
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Scheme 204. Quinoline-Fused Porphyrins via Cadogan Cyclizationa
Reagents and conditions: (a)1260 P(OEt)3; (b) DMF/POCl3, 90%; (c) TsOH, toluene, .
Scheme 205. Synthesis of Quinoline-Annulated Porphyrinsa
Reagents and conditions:1262 (a) NH2OHHCl, pyridine, rt; (b) p-TSA, toluene, reux.
Scheme 206. Oxidative Fusion Reactions of meso-(Diarylamino)porphyrinsa
Reagents and conditions: (a)1265 10 equiv of FeCl3, 10 equiv of DDQ, CH2Cl2/MeNO2, 15 min; (b) (1) TFA, H2SO4, rt, 2 h, (2) excess of
Zn(OAc)22H2O, CH2Cl2, 1 h; (c) 20 equiv of FeCl3, 20 equiv of DDQ, CH2Cl2/MeNO2, 4 h; (d) HCOOH, NEt3, Pd(OAc)2/SPhos, toluene, 120
C, 5 h; (e) 20 equiv of FeCl3, 20 equiv of DDQ, CH2Cl2/MeNO2, 1.5 h.
system 204.3 accompanied by a small amount of 204.2 formed

by retro-formylation. 204.3 and its corresponding free base
both showed high absorbance in the therapeutic window (700

800 nm), whereas the corresponding Pd(II) complex was able
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to generate singlet oxygen eciently, thus demonstrating its

potential utility in photodynamic therapy.
A synthesis of bis-quinoline-annulated porphyrins, starting
from the generally useful porphyrin-2,3-dione 205.1,1261 was
reported by Bruckner and co-workers (Scheme 205).1262 The
reaction of 205.1 with a ca. 100-fold excess of NH2OHHCl
formed the monoxime 205.2 as the major product and a small
amount of bisoxime 205.3. Treatment of 205.2 with a strong
acid produced the quinolineoxochlorin framework 205.4,
which gave the corresponding oxime 205.5 in a subsequent
reaction with NH2OHHCl. The nal acid-catalyzed annulation
yielded the bis-annulated 205.6. Bisoxime 205.3 could also be
directly converted into the bisquinoline 205.6, albeit in a
signicantly lower yield (12%) in comparison to the stepwise
protocol (40% in three steps). It was determined that in the
direct bis-annulation, oxadiazole 205.7 formed as the major
product. The UVvis spectrum of 205.6 was bathochromically
shifted with an optical bandgap of 775 nm. Recently, Bruckner
et al. utilized the same synthetic pathway to the synthesis of
monoquinolino annulated metaloporphyrins.1263 Metalation of
205.6 had to be performed after the annulation step because
the reaction of 205.8 and 205.9 complexes with p-TSA led
preferentially to the expansion of the oxidized pyrrole ring via
Beckmann rearrangement, as had been reported previously.1264
The UVvis spectra of the nickel and palladium complexes of
205.6 are qualitatively similar to the free base spectrum,
showing a broadened Q-band region with no detectable
splitting of the Soret band.
The possibility of developing fused porphyrins from mesoamino-substituted precursors was explored in 2013 by Osuka,
Yorimitsu, Kim, et al.1265 The reaction of the noncyclic
arylamine 206.1 with FeCl3 and DDQ led to the formation of
the aminophenylene-fused derivative 206.2 in good yield
(Scheme 206). Double fusion could only be achieved under
more forceful conditions, which yielded a dichlorinated doubly
fused porphyrin 206.4. Dechlorination of 206.4 was carried out
by reaction with HCOOH and NEt3 in the presence of the
Pd(OAc)2/SPhos catalytic system. The Soret and Q-bands of
206.3 and 206.6 are red-shifted, with the low-energy maxima at
640 and 629 nm, respectively. TPA values determined by openaperture Z-scan measurements at 1200 nm were 170, 250, and
430 GM for 206.1, 206.2, and 206.5, respectively. The
electrochemical HOMOLUMO gaps of 206.2 and 206.5
were 1.98 and 1.93 eV, respectively, smaller than measured for
the parent 206.1 (2.17 eV). In contrast to 206.1, the oxidative
coupling of 206.7ab with FeCl3 and DDQ aorded
unexpected fusion products 206.8ab with two peri-condensed
meso-3,5-di-tert-butylphenyl groups. The fusion of the phenoxazine/phenothiazine substituent could not be accomplished.
The diculties associated with coupling of meso-amino
groups were further demonstrated in related work by Gryko
and Nowak-Krol (Scheme 207).1266 Under typical conditions
(FeCl3, CH2Cl2/MeNO2), the attempted coupling of 207.1 led
to a complex mixture of products including chlorinated
porphyrins, whereas the use of DDQ/Sc(OTf)3 resulted only
in the decomposition of the starting material. An alternative
oxidant, Fe(ClO4)3H2O, provided moderate yields of the
monoconjugated derivative 207.2, not contaminated by
chlorinated side products. Bis(3,5-dimethoxyphenyl)aminesubstituted 207.3 underwent oxidation into the fused product
207.4 under milder conditions. The electrochemical HOMO
LUMO gap of 207.2 was 1.90 eV, that is, slightly smaller than
the value for parent 207.1 (2.08 eV), corresponding to a
Scheme 207. Oxidative Aromatic Coupling of mesoArylamino-porphyrinsa
Reagents and conditions:1266 (a) Fe(ClO4)3H2O, MeNO2, DCM, rt,

72 h; (b) FeCl3, MeNO2, DCM, rt, 3 min.
a
bathochromic shift of the lowest energy absorption band of ca.

35 nm.
Recently, Osuka, Yorimitsu, et al. showed that meso,oligohaloporphyrins are viable precursors for the synthesis of
fused meso-aminoporphyrins (Scheme 208).1267 The reaction of
Scheme 208. Synthesis of Diphenylamine-Fused Porphyrina
Reagents and conditions:1267 (a) diphenylamine, NaO-t-Bu, DMF,

100 C, 7 h.
208.1 with diphenylamine in the presence of NaO-t-Bu

aorded the fused porphyrin 208.2 in one step in 81% yield.
The expected SNAr substitution product was not detected
under these conditions. The precise mechanism of this
transformation remains unclear, although the formation of an
intermediate porphyrinyl radical via electron transfer to iodide
and subsequent dissociation of I was presumed, on the basis of
previous reports.12681270
The preparation of porphyrins bearing chelating peripheral
groups fully conjugated with the macrocyclic -system was
described by Callot, Ruppert, et al.1271 The initially tested
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Scheme 209. Porphyrins with Peripheral Conjugated Chelates and Their Pd Complexesa
Reagents and conditions:1271 (a) P(OEt)3, 1,2-dichlorobenzene, 155 C; (b) POCl3, DMF, CH2Cl2; (c) Lawessons reagent, benzene, 75 C; (d)
Pd(OAc)2, 1,2-dichloroethane.
Scheme 210. Quinolino-Fused Porphyrins from Azidotetraarylporphyrinsa
Cadogan reaction on a meso-ortho-nitroaryl substituted

porphyrin did not yield satisfactory results; however, clean
cyclization was achieved with -nitroporphyrins 209.1 (Scheme
209). When the nickel derivative 209.1 was treated by excess of
triethyl phosphite at 155 C, enamine 209.2 was obtained as
the major product (75%). Under VilsmeierHaack conditions,
the formylation of enamine 209.2 proceeded smoothly to give
enaminoaldehyde 209.3 in 90% yield. Lawessons reagent was
then used to convert the carbonyl group of 209.3 into the
thiocarbonyl. The reaction of the resulting enaminothioaldehyde 209.4 with Pd(OAc)2 led to the formation of two
isomeric complexes, 209.5ab and 209.6ab, characterized,
respectively, by the trans and cis conguration at Pd. In
contrast, the reaction of enaminothioaldehyde 209.4 under the
same conditions led exclusively to the cis isomer 209.6c. The
electronic spectra of isomers 209.5ab and 209.6ab were
almost superimposable, with broadened and split Soret bands
and bathochromic shifts of the lower wavelength bands relative
to the free 209.3 and 209.4. The UVvis absorption spectrum
of 209.6c exhibited an even larger red shift up to 714 nm.
In a related approach, reported by Chen et al. in 2007,
thermal decomposition of -azidotetraarylporphyrins similarly
led to the formation of fused six-membered rings (Scheme
210).1272 In this work, a variety of azido derivatives 210.1ad
were conveniently synthesized by the classical conversion of the
amino groups through diazotization and subsequent treatment
with sodium azide. Depending on the nature of the
substituents, the yields for various N-containing fused
porphyrins 210.2ad varied from 60% to 85%.
In 2009, Osuka, Shinokubo, and Shinmori reported the
synthesis of pyridine-fused oxobenzochlorins 211.3ac
(Scheme 211).1273 The zinc(II) dehydropurpurin 211.1
(discussed in more detail in section 7.4) was eciently
converted into 3,5-dibenzoylporphyrin 211.2a by photochemical oxidative cleavage of the outer double bond. The
treatment of 211.2a with ammonium acetate at 130 C in
toluene/AcOH for 2 days furnished a chlorin derivative 211.3a
in 60% yield. In a similar manner, Ni-pyridochlorin and the free
base, 211.3c and 211.3b, were also synthesized in 65% and
Reagents and conditions:1272 (a) toluene, reux, 2 h.
40%, respectively. The absorption spectra of oxopyridochlorins

were strikingly altered in comparison with the typical features
of porphyrins. The metal complexes 211.3a and 211.3c
exhibited structured Q-bands at 753 and 767 nm, respectively.
In each case, the Soret band was split (e.g., 403 and 477 nm for
211.3a). Free base 211.3b showed a split Soret band at 414 and
448 nm, and dierently structured Q-bands at 690 and 785 nm.
The absorption spectra of oxopyridoporphyrins 211.3 thus
covered a considerable part of the PDT therapeutic window,
and the compounds were shown to enable singlet oxygen
generation.
A doubly fused porphyrin was obtained by Jeandon and
Ruppert by sequential application of two Cadogan cyclizations.1274 The rst supplementary ring was closed by reacting 2nitro-TPP 212.1 with triethyl phosphite, in a manner described
above (Scheme 212). The second ring closure required the
protection of the outer nitrogen of 212.2 with the Boc group,
prior to the Cadogan reaction. The resulting bis-quinolinofused porphyrin 212.5, bearing an internal and external
coordination site, was easily demetalated, and free base 212.6
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Scheme 211. Synthesis of Oxopyridochlorina
a
Reagents and conditions:1273 (a) air, light; (b) HCl; (c) Ni(acac)2; (d) NH4OAc, toluene/AcOH, 130 C, 2 days; (e) NaBH4, CH2Cl2/MeOH; (f)
air.
Scheme 212. Bis-quinolino-Fused Porphyrinsa
Reagents and conditions:1274 (a) P(OEt)3; (b) (1) NaH, THF, rt, 30 min, (2) isobutyl chloroformate, rt, 1 h; (c) LiNO3, Ac2O, AcOH, CHCl3, rt,
90 min; (d) 1,2-dichlorobenzene, reux, 30 min; (e) TFA, H2SO4, rt, 3 h.
was isolated in an almost quantitative yield. Both nickel

porphyrins 212.5 and 212.6 absorbed in the 650800 nm
window with very high extinction coecients (from 15 000 to
22 000 M1 cm1 in the case of 212.5), which made them
potentially useful in PDT applications.
7.2.4. Pyrano- and Thiopyrano[cd]fused Systems.
Reactions of nickel(II) meso-tetraalkylporphyrins with elemental sulfur were performed in 1997 by Callot and co-workers to
mimic geochemical processes.1275 Fusing the reactants at 200
C resulted in the formation of product mixtures, from which
thiopyran-fused macrocycles C58.1 were isolated chromatographically (Chart 58). The reaction of tetra(sulfophenyl)porphyrin with fuming H2SO4 was reported by Dixon et al. to
produce the cyclic sulfone C58.2, a potential precursor to
conjugated thiopyran derivatives.1276 A thiopyran-fused subporphyrin C58.3 was recently described by Osuka, Kim, and
co-workers.1277
Heating of [26]hexaphyrin 213.1 in acetic acid led to the

formation of the benzopyran-fused [28]hexaphyrin 213.2
(Scheme 213), accompanied by the corresponding nonfused
[28]hexaphyrin.1278 Compound 213.2 had a stable Mobius
conformation, and exhibited an aromatic character over a wide
temperature range. The oxidation of 213.2 with DDQ
Scheme 213. Benzopyran-Fused Hexaphyrinsa
Chart 58. Thiopyran-Fused Porphyrins and Their

Derivatives
Reagents and conditions:1278 (a) AcOH, 130 C, 6 h; (b) DDQ; (c)

NaBH4.
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Scheme 214. Synthesis of Doubly meso--Linked Diporphyrinsa
Reagents and conditions: (a)1279 TeCl4, DCM, rt; (b)1280 1 equiv of BAHA, CHCl3, rt; (c) 1.2 equiv of BAHA, CHCl3, rt; (d)1281 BAHA, CHCl3,
rt.
Scheme 215. Synthesis of meso- Doubly Linked Porphyrin Tapesa
a
Reagents and conditions: (a)1282 2 equiv of DDQ, 2 equiv of Sc(OTf)3, toluene, 50 C; (b)1225 AuCl3, AgOTf, 1,2-dichloroethane, rt, 23 min; (c)
HCO2H, Et3N, Pd(PPh3)4, toluene, reux.
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Scheme 216. Synthesis of meso- Doubly Linked Zn(II) Porphyrin Trimersa
Reagents and conditions:1284 (a) 2 equiv of DDQ, 0.5 equiv of Sc(OTf)3, toluene, 30 C, 72 h.
214.1 with the DDQscandium(III) triate oxidant system.1282

The reaction mixture was puried, and the following products
were separated: singly linked diporphyrin 215.1 (27%), meso-
doubly linked dimer 215.2 (8%), trimer 215.3 (6%), tetramer
215.4 (5%), and pentamer 215.5 (4%, Scheme 215). The
lowest energy bands in the absorption spectra were
progressively red-shifted upon increase of the number of
porphyrin units: 741 nm for 215.2, 892 nm for 215.3, 996 nm
for 215.4, and 1075 nm for 215.5. The one-electron oxidation
potential of 215.2 was determined to be 0.56 V, which is lower
than the values for parent monomer 214.1 (0.74 V) and singly
linked compound 215.1 (0.76 V) but higher than that
measured for the corresponding triply bonded dimer (0.46 V,
cf., section 7.3). These results suggested that the energy level of
the HOMO orbital was lifted upon expansion of the -system
of the porphyrin, a hypothesis that was conrmed by oxidation
potentials measured for longer oligomers (from 0.44 V for
215.3 to 0.35 V for 215.5). TPA cross sections for the lowestenergetic bands of 215.25 were found to increase from 8000
(215.2) to 41400 GM (215.5) with the increasing length of the
array.1283
Coupling of the monobromoporphyrin 215.6, mediated by
the AuCl3AgOTf combination, was reported by Osuka and
co-workers to provide high yields of the porphyrin dimer
215.7.1225 This reagent was found to be eective at ambient
conditions, and with short reaction times. Additionally, an
ecient Pd-catalyzed debromination of the meso position was
developed, which enabled using bromine as a meso-protecting
group in porphyrins.
Zn(II) porphyrin trimer 216.1 and its syn isomer 216.2 were
synthesized by DDQSc(OTf)3 oxidation of the corresponding
meso- singly linked porphyrin precursors 216.3 and 216.4
(Scheme 216).1284 The UVvis absorption spectrum of anti
isomer exhibits peaks at 427, 852, and 963 nm. The spectrum
of 216.2 is considerably dierent, showing six major bands at
422, 522, 604, 734, 927, and 982 nm, with molar extinction
coecients that are apparently smaller than those of 216.1.
Interestingly, one of the isomers, 216.2, showed detectable
proceeded to exclusively give the planar Huckel aromatic

[26]hexaphyrin 213.3, which slowly isomerized under ambient
conditions to reach the stationary 4:1 mixture of 213.3 and
213.4. Interestingly, the reduction of this mixture with NaBH4
gave 213.2 quantitatively.
7.2.5. Benzo-Fused Porphyrin Oligomers. The rst
example of a peri-condensed porphyrin dimer, named [2]porphyracene, was reported in 1999 by Sakata, Sugiura, et
al.1279 Compound 214.2 was obtained in an unusual reaction
between [5,15-bis(3,5-di-tert-butylphenyl)porphyrinato]nickel
214.1 and tellurium(IV) tetrachloride (Scheme 214). The
electronic spectrum of 214.2 showed a considerable increase in
the intensity of Q-bands in comparison with 214.1, with the
lowest-energy absorption at 743 nm, and a weaker Soret band.
A similar type of coupling was achieved almost simultaneously
by the Osuka group with the aid of one-electron oxidants.1280
The reaction of 214.1 with an equivalent amount of tris(4bromophenyl)aminium hexachloroantimonate (BAHA) produced a mixture of dimeric, trimeric, and tetrameric porphyrins,
of which only the dichlorodiporphyrin 214.2a was successfully
isolated. In the reaction of 214.1a with the same oxidant,
compound 214.2a was also obtained in 68% yield. Similar
doubly meso--linked diporphyrin products 214.2bd were
obtained in the reaction of Pd-porphyrin 214.1b, with the
product ratio dependent on the reaction time and amount of
BAHA used. The one-electron oxidation potentials of 214.2b,
214.2c, and 214.2d (0.57, 0.59, and 0.62 V, respectively) were
signicantly lower than that of monomer 214.1b (0.82 V). The
bis-Ni analogue of 214.2b revealed a rued conformation in
the solid state. In contrast to the Ni and Pd complexes, the Znand free base derivatives 214.1cd produced exclusively the
singly linked porphyrin 214.3b, whereas the oxidation of the
Cu complex 214.1e provided a mixture of meso- doubly linked
diporphyrin 214.2f (25%), mesomeso linked dimer 214.3c
(33%), and the meso-chlorinated monomer 214.4 (24%).1281
In subsequent work from the Osuka group, meso- doubly
linked porphyrin oligomers were produced by oxidation of
Ni(II)-complex 5,15-bis(3,5-di-tert-butylphenyl)porphyrin
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Chart 59. Indene-Fused Analogues of meso- Doubly Linked Zn(II) Porphyrin Arrays
Scheme 217. Synthesis of para-Phenylene-Bridged Porphyrin Tapesa
(a)1286 BBr3, CH2Cl2, 20 C, then Zn(OAc)2; (b) CH2(CN)2 (1000 equiv), TiCl4, CH2Cl2; (c) Pd(PPh3)4, K3PO4, DMF, 155 C.
Scheme 218. Synthesis of a p-Quinodimethane-Bridged Porphyrin Dimera
Reagents and conditions: (a)1287 triisopropylsilylethynylmagnesium bromide, THF, rt, 48 h; (b) 4-tert-butylphenylmagnesium bromide, THF, rt, 48
h; (c) (1) excess BF3Et2O, CH2Cl2, 10 min, (2) air oxidation.
uorescence in the NIR region (max = 1048 nm), upon

excitation at 420 nm. TPA cross-section values at 1850 nm
were measured to be 16 800 and 7900 GM, for 216.1 and

216.2, respectively.
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Scheme 219. Benzo-Fused Corrole Dimersa
In 2010, Osuka, Kim, et al. synthesized meso- doubly linked

Zn(II) porphyrin arrays fused with indene moieties C59.13
via intramolecular oxidative DDQSc(OTf)3-mediated coupling of singly bonded precursors (Chart 59).1285 The fusion of
indene moieties at the porphyrin unit, which occurred
concomitantly with the formation of interporphyrin bridges,
caused steric repulsions and further expansion of the elongated
-system, leading to decreased HOMOLUMO energy gaps.
The S1-state lifetimes for the C59.13 arrays showed double
exponential decays with a common value of the short time
constant (2.5 ps) and the second decay time constant of 10.5,
8.4, and 10.3 ps, respectively. In comparison to the values
measured under the same conditions for analogues possessing
no indene units, excited-state lifetimes of the C59.13 arrays
are shorter. TPA cross-section measurements yielded values of
11 600, 23 600, and 17 100 GM, for C59.1, C59.2, and C59.3,
respectively.
The anthracene-1,5-dione-fused bisporphyrin 217.2 was
obtained by Anderson and co-workers using a double
intramolecular FriedelCrafts acylation of 217.1a (Scheme
217).1286 Interestingly, subsequent reaction with malononitrile
gave the unexpected bisannulated compound 217.3. In the
same work, an intramolecular Heck-type coupling performed
on 217.1b was utilized for the synthesis of the cyclopenta[cd]fused dimer 217.4 in 20% yield. The longest wavelength
absorption Q-band of dimer 217.4 was observed at 1077 nm,
whereas the cross-conjugated dimer 217.2 exhibited the
corresponding absorption maximum at 907 nm. Compound
217.2 exhibits measurable uorescence, mirroring the lowest
Q-band (960 nm, 1.7% quantum yield). In contrast,
luminescence from 217.4 was undetectable. Surprisingly, both
dimers had essentially identical electrochemical HOMO
LUMO gaps.
In subsequent work by Wu et al., analogously designed
diketobisporphyrins 218.2ab were envisaged as precursors to
p-quinodimethane-bridged porphyrin dimers (Scheme
218).1287 Interestingly, however, addition of either aryl or
alkynyl Grignard reagents resulted in Michael addition to the
pyrrole -positions adjacent to the carbonyl groups (218.3).
The quinodimethane target 218.1 was successfully prepared by
intramolecular FriedelCrafts alkylation of the diol-linked
dimer 218.4 with concomitant oxidation in air. 218.1 showed
intense one-photon absorption (OPA, max = 955 nm, =
45 400 M1cm1) and a large TPA cross-section (2080 GM at
1800 nm). In CV and DPV measurements, porphyrin 218.1
showed four quasi-reversible oxidation waves with half-wave
potentials (Eox1/2) at 0.01, 0.14, 0.6, and 0.93 V and two quasireversible reduction waves with half-wave potentials (Ered1/2) at
1.14 and 1.36 V (vs Fc+/Fc). Compound 218.1 exhibited a
high-lying HOMO energy level (4.70 eV) and a small energy
gap (0.86 eV).
A benzo-fused corrole dimer 219.2 was obtained by oxidative
coupling of the mesomeso-linked precursor 219.1 (Scheme
219).1288 219.2 was treated with sodium borohydride to
provide the reduced dimer 219.3, wherein each macrocyclic
subunit has the typical corrole-like oxidation level. 219.3 was
oxidatively labile and reversed to 219.2 in the presence of air.
Compounds 219.2 and 219.3 were described, respectively, as
nonaromatic and aromatic, on the basis of their optical spectra
and magnetic properties. The unusual stability of 219.2 was
ascribed to the presence of two direct connections between the
individual corrole units.
Reagents and conditions:1288 (a) DDQ, CHCl3, reux, 1 h; (b)

NaBH4, THF/MeOH, 0 C, 15 min; (c) air oxidation.
7.2.6. Oxonaphtho-Fused Porphyrins and Benzooxochlorins. During the attempted demetalation of tetraphenylporphyrins bearing a formyl group at the position (e.g.,
220.1), the cyclization of the adjacent meso and substituents
was observed by Henrick et al., and the resulting verdin 220.2
was characterized crystallographically (Scheme 220).1289 The
Scheme 220. Synthesis of Oxonaphtho-Fused Porphyrinsa
Reagents and conditions: (a)1289 acidic conditions (TFA); (b)1294 pchloranil, 70% TFA in water, benzene; (c)1294 AlCl3, LiAlH4, ether.
formation of similar compounds was also reported by Buchler

et al. in their investigations of the Vilsmeier reaction,1290 and
the chemistry was further explored by Callot and coworkers,1291 Dolphin et al.1292 (cf., Chart 60), and Ishkov et
al.1293 The latter group proposed a more ecient route to
220.2, involving the use of p-chloranil. Further studies by
Ishkov revealed that the treatment of 220.1 with a saturated
solution of p-chloranil in boiling benzene in the presence of
70% aqueous triuoroacetic acid provided as the major product
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Scheme 221. Naphtho-Fused Porphyrins Bearing Peripheral Chelating Groupsa
Reagents and conditions:1271 (a) (1) 4-H-4-amino-1,2,4-triazole, NaOH, (2) CF3COOH; (b) excess Pd(acac)2.
the isomeric system 220.3, with the carbonyl group located at

the adjacent -position of the macrocycle (71% yield).1294 Both
220.2 and 220.3 underwent reduction with a 1:1 AlCl3LiAlH4
system.
Enaminoketones 221.2ab bearing a carbonyl group at the
macrocyclic periphery can act as both internal and external
ligands (Scheme 221).1271 The starting ketones 220.3, 221.1
were obtained from -formyltetraarylporphyrins according to
the procedure described by Ishkov.1294 Treatment of complexes
221.1 with 4-amino-4H-1,2,4-triazole gave the desired ligands,
which however could not be converted into the thio derivatives
by using Lawessons reagent. Metalation of enaminoketones
221.2 yielded monomeric and dimeric complexes, 221.3 and
221.4, respectively, characterized by hypsochromically shifted
electronic spectra.
Porphyrins acting as a fully conjugated aromatic system,
capable of simultaneous external and internal ligation, were
described by Callot, Ruppert, et al.1295 Such ligands were
obtained from ketone derivatives 222.1, which were reacted
with various nitrogen nucleophiles (Scheme 222). Under mild
acid catalysis, reagents of the general composition H2NX (X =
OH, NHTs, OSO3H) gave the enaminoketone 222.2 in
variable yields. The highest yield (90%) was observed in the
reaction with the hydroxylamine-O-sulfonic acidAcOH
NaOAc system in reuxing dichloromethane. External metalation of 222.2a with an excess of nickel acetyloacetonate gave
the trinuclear complex 222.3. Similarly, several trimetallic
bisporphyrins were prepared (Ni/Cu/Ni; Ni/VO/Ni; Ni/
Pd/Ni). In the electronic absorption spectrum, the lowest
energy band of 222.3 was shifted to 700 nm ( = 33 000 dm3
mol1 cm1) in comparison to the band observed at 649 nm (
= 18 500 dm3 mol1 cm1) for Ni-222.2a. In further
investigations by the same group, it was found that the pyrrolic
position next to the acyl group could be eciently functionalized, yielding products with peripheral coordinating sites.1296
A thioketone analogue of 222.2 was also obtained and used for
the preparation of the Ni2Pd complex 222.4.1271 Porphyrin
enaminoketones were also used as ancillary ligands in
ruthenium complexes 222.5ac.1297 The coordination of
ruthenium to the porphyrins induced a blue shift of the Soret
band maxima (especially for 222.5b, = 20 nm) as well as a
decrease of its intensity, while new absorption bands appeared
in the 500600 nm range. A signicant red shift of the
absorption bands was observed for the enaminothioketones and
222.6ac.1298
Porphyrins bearing two divergent external coordination sites
were subsequently developed with the prospect of building
Scheme 222. Preparation of Conjugated Trimetallic Dimeric

Porphyrinsa
a
Reagents and conditions: (a)1295 hydroxylamine-O-sulfonic acid,
AcOH, AcONa, CH2Cl2, reux; (b)1295 excess of Ni(acac)2, toluene,
reux.
higher metal-connected oligomers.1299 These bis-functionalized

porphyrins, such as the centrosymmetric 223.5 (Scheme 223),
were prepared using an alternative route, which involved
cyclization of two meso-o-carbomethoxyphenyl substituents,
followed by enamine formation. This synthetic route was also
used for the preparation of monoketones in high yields (e.g.,
223.4).1300 Oligonuclear complexes 223.69 were prepared
from bis-amine ligands in reactions with palladium(II)
acetyloacetonate.1299 The electronic spectra of compounds
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Scheme 223. Porphyrin Oligomers Linked by Metal Ionsa
a
Reagents and conditions: (a)1300 LiOHH2O, water, dioxane, reux, 24 h; (b)1300 (1) oxalyl chloride, benzene, rt, 2 h, (2) SnCl4, rt, 1 h; (c)1300 (1)
TFA, rt, 45 min, 97%, (2) 4-amino-4H-1,2,4-triazole, toluene, EtOH, NaOH, reux, 1 h, (3) Ni(acac)2, toluene, 80 C, 24 h, 92%.
Scheme 224. Preparation of Isomeric Fused Bis-acylporphyrinsa
Reagents and conditions:1302 (a) (1) LiOH, (2) (COCl)2, (3) SnCl4; (b) (1) H2SO4, (2) Ni(acac)2, (3) (COCl)2, (4) SnCl4.
producing 7-membered rings, was reported by Jux, Roder, et

al.1301
The method described above was systematically investigated
in subsequent work of Callot, Ruppert, et al., who described the
preparation of six cyclic diketones derived from meso-
223.68 showed large red shifts as compared to parent

porphyrin 223.5. The most signicant shift was observed on
the two lowest-energy bands in the case of trimer 223.8 (690
nm vs 789 nm, and 758 nm vs 881 nm, in 223.5 and 223.8,
respectively). An extension of the above cyclization approach,
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Scheme 225. Synthetic Route to Porphyrinic Spiro Dimersa
Reagents and conditions: (a)1304 acetic anhydride, SnCl4, CH2Cl2, rt, 5 min; (b)1304 air, pyridine; (c)1304 pivalic anhydride, SnCl4, CH2Cl2, rt, 4
min.
tetraarylporphyrins.1302 The nickel complexes of diketones

224.3, 224.4, and 224.5 were prepared from the porphyrin
224.1 in 86% total yield, according to the previously reported
procedure (Scheme 224).1299,1300 Reacting isomer 224.2 under
the same conditions gave compounds 224.6 and 224.7 in 36%
and 40% yields, respectively. Cu analogues of diketones 224.3
and 224.7 were also accessible from -cyanoporphyrins via
acid-catalyzed condensations. Moreover, the phenalenedionefused diketone 224.9 was prepared from porphyrin 224.8 in a
37% yield. Demetalation of the Ni complexes could not be
accomplished, which prompted the attempts to perform
carboxylic cyclizations on free base porphyrins. The latter
approach produced the free-base analogues of 224.4 and 224.7
in moderate yields (11% and 20%, respectively). All diketones
showed Soret bands in the 472524 nm range and strongly
red-shifted Q bands (up to 826 nm). Subsequent derivatization
of diketones 224.47 and 224.9 enabled the preparation of the
corresponding enaminoketones and enaminothioketones.1303
In these systems, the thionation was observed to reduce the
HOMOLUMO gaps of the porphyrins.
Attempted acylation of nickel(II) meso-tetraarylporphyrins
under FriedelCrafts conditions was shown by Callot et al. to
provide the porphyrinic spiro dimer 225.3 (Scheme 225).1304
In contrast, the reaction of nickel porphyrin 225.1 with acetic
anhydride and SnCl4 as a Lewis acid gave compound 225.2 as
the major product. When exposed to air in solution, 225.2 was
converted into a stable spiro dimer 225.3 possessing three
additional six-membered rings. This reaction proceeded faster
in pyridine and could be run on the crude product from the
acylation step, to give 225.3 in 4558% yield. When pivalic
anhydride was used in the acylation of 225.1, tertiary alcohol
225.4 was isolated (15%), along with the ketone 225.5 (5%)
and recovered starting material (13%).
To suppress the formation of dimer 225.3, anhydrides
containing no -hydrogens were explored as acylating
agents.1305 The use of benzoic anhydride induced a complete
change in the course of the reaction and led to the formation of
the green porphyrin 226.2 and the dark blue corrole 226.3, in
addition to several minor products (Scheme 226). The initial
low yield of 226.3 (ca. 36%) was optimized by changing the
reaction conditions and structure of the starting material (24%
for R1 = OEt and M = Ni). The use of the NiII complex proved
to be crucial, because the copper(II) species 226.1 did not
Scheme 226. Acylation-Induced Benzannulation and

Macrocycle Contractiona
Reagents and conditions:1305 (a) (1) (PhCO)2O, SnCl4, (2) H2O,

NaHCO3, (3) (PhCO)2O, pyridine, DMAP, air.
undergo contraction to produce the corrole, yielding only the

fused porphyrin 226.2. Further optimization of this reaction
was performed, revealing the formation of small amounts of
lactonic seco-porphyrins under certain conditions.1306 Formation of oligomeric corrole derivatives during attempted
nitration of 226.3 was subsequently observed by Callot et
al.1307 In contrast to the Ni complex, which was photochemically inactive, the Pd complex 226.2 was shown to be an
ecient photosensitizer for singlet oxygen generation.1308
7.2.7. Indole- and Carbazole-Based Porphyrinoids.
Benzo[cd]fusion at a porphyrin ring formally results in the
formation of an indole substructure, whereas two fusions of this
kind performed at a single pyrrole ring produce a carbazole
motif. An alternative synthetic approach to benzo[cd]porphyrinoids can thus be envisaged, relying on the assembly
of indole or carbazole components. In 2010, the rst example of
a porphyrin-related macrocycle 227.2, consisting of directly
linked pyridine and carbazole moieties, was reported by Mullen
and Norouzi-Arasi et al. (Scheme 227).1309 The macrocycle was
obtained via SuzukiMiyaura cross-coupling reaction of
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ingly, these systems are highly uorescent (F = 0.780.61),

apparently because of their conformational rigidity. In contrast,
the absorption spectrum of the porphyrin-like 228.8 displays
intense Q-like bands with very large bathochromic shifts (845,
934, and 1049 nm). The macrocyclic conjugation in 228.8 can
be described using the usual porphyrin like [18]annulenoid
conjugation pathway, with contributions of larger paths
involving the peri-fused benzene rings.
The addition of ethynyl substituent groups to the periphery
of carbazole-based core-modied porphyrins was seen as a
means of modifying their optical and electronic properties.1312
Treatment of 228.7 with NBS gave the tetrabrominated
compound 229.1 (Scheme 229) in 88% yield. The Stille
coupling reaction of 229.1 with tributyl(trimethylsilylethynyl)tin provided the tetrakis-substituted product 229.2. In the nal
step, compound 229.2 was oxidized to 229.3 using MnO2. In
the related derivative 229.7, bearing ethynyl chains on the
carbazole moieties, these substituents were introduced prior to
macrocycle formation. The ethynyl substituents in 229.3 and
229.7 led to marked reduction of the optical and electrochemical HOMOLUMO gaps relative to the unsubstituted
analogues. Even longer oligoethynyl substituents were introduced in subsequent work, to produce systems 229.8 and 229.9
with distinctly altered optical signatures.1313
Maeda and Yoshioka described the synthesis of porphyrinoids consisting of carbazole, indolone, and thiophene
moieties.1314 In the rst synthetic step, functionalized carbazole
230.1 was coupled with an aniline derivative via the
Sonogashira reaction (Scheme 230). The subsequent InCl3catalyzed cyclization of 230.2 produced the bis(7-iodoindol-2yl)-substituted carbazole 230.3, which was converted into the
diethynyl species 230.4 in the following step. The subsequent
Glaser cyclization yielded the aromatic dione 230.5 instead of
the expected 230.6. Finally, the Stille coupling between 230.3
and (tributylstannyl)thiophene aorded the core-modied
system 230.7. Interestingly, it was found that 230.7 could be
converted into the dioxygenated product 230.8 through MnO2mediated oxidation. The UVvis absorption spectrum of 230.7
exhibited absorption primarily in the ultraviolet range, while the
spectra of 230.5 and 230.8 extended into the visible region.
The complexation reaction of 230.8 with palladium(II) acetate
followed by ligand exchange produced 230.9 in an almost
quantitative yield. Compounds 230.5 and 230.79 were
considered weakly aromatic. The electronic absorptions of
the diketo systems showed extended absorption in the vis and
NIR regions of the spectrum (up to 800 nm for 230.9).
In 2012, Mullen et al. reported the successful extension of
their original approach1309 to the synthesis of the pyrrole
carbazole system 231.3 containing a complete porphyrin
substructure (Scheme 231).1315 In contrast to the Osuka
groups strategy,1311 this route did not require protection of the
pyrrole NHs, relying instead on a 4-fold SuzukiMiyaura crosscoupling reaction between carbazole 231.1 and pyrrole 231.2.
When performed at high dilution, this reaction produced the
macrocycle 231.3 in 10% yield. Compound 231.3 featured two
local maxima at 307 and 400 nm in its absorption spectrum and
blue uorescence emission (427 nm, F = 0.68). Macrocycle
231.3 was subjected to MnO2 oxidation, yielding an unstable
product 231.4, displaying bathochromically shifted bands in the
absorption spectrum (846, 945, and 1076 nm), indicative of
macrocyclic aromaticity.
In 2013, bis-thiophene-bridged carbazole dimer 232.3 and
trimer 232.4 were obtained by Masuda and Maeda through the
carbazole 227.1 with 2,6-dibromopyridine. The molecular

design retains the inner circuit of the porphyrin ring, and the
number of inner NHs, providing a similarly sized macrocyclic
cavity as well as the ability to bind metal ions. The coordination
properties of 227.2 were demonstrated by the formation of a
cobalt complex 227.3. Compound 227.2 showed two
absorption maxima at 313 and 372 nm and blue uorescence
emission with a maximum at 402 nm (F = 0.36). The
emission of the free ligand was quenched upon complexation
with cobalt(II). The UVvis spectrum of 227.3 exhibited a
bathochromic shift (331 and 425 nm) in comparison to the free
base. In subsequent work, 227.3 was sublimed under ultrahigh
vacuum onto a ferromagnetic Ni(001) thin lm grown on a
Cu(001) single crystal.1310 The adsorbed molecules were
randomly distributed on the surface with their macrocyclic
cores parallel to the substrate. The adsorbed complex was
found to possess an exchange-stabilized magnetic moment.
Both experimental and theoretical studies suggested that this
induced magnetic moment is a general eect, not limited to the
previously observed cases of metalloporphyrins and metallophthalocyanines.
Scheme 227. Synthesis of a Hybrid PyridineCarbazole
Porphyrinoida
Reagents and conditions:1309 (a) 2,6-dibromopyridine, Pd(PPh3)4;

(b) Co(OAc)2, reux, DMF.
A multiple annulation strategy enabling the synthesis of

porphyrinoids from 1,3-butadiyne-bridged cyclic carbazole
oligomers 228.2-3 was developed by Maeda and co-workers
(Scheme 228).1311 The Glaser coupling of carbazole 228.1
provided three isolable oligomeric products: dimer 228.2
(35%), trimer 228.3 (4.9%), and tetramer 228.4 (7.6%). A
CuCl-catalyzed annulation of 228.2 with anilines aorded Narylpyrrolylene-bridged carbazole dimers 228.5ac. These
dimers, which can be regarded as cross-conjugated isophlorin
analogues, could not be oxidized to the porphyrin-like state
characterized by macrocyclic aromaticity. An analogous aniline
cyclization performed on the trimer 228.3 yielded the
hexaphyrin-like macrocycle 228.6. Similar annulation reactions
of 228.2 and 228.3 with sodium sulde produced porphyrinoids 228.7 and 228.9, respectively. The oxidation of 228.7
with MnO2 furnished the corresponding aromatic porphyrin
analogue consisting of thiophenecarbazole moieties 228.8.
The absorption spectra of 228.5 and 228.6 were similar, with
the most red-shifted bands in the 401424 nm range, reecting
the nonconjugated character of these macrocycles. InterestEV
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Scheme 228. Synthesis of Carbazole-Containing Porphyrinoids by a Multiple Annulation Strategya
Reagents and conditions:1311 (a) Cu(OAc)2, air, pyridine, toluene, rt, 3 d; (b) RNH2, CuCl, mesitylene, reux, 24 h; (c) Na2S9H2O, THF, reux,
24 h; (d) MnO2, CH2Cl2; (e) Na2S9H2O, p-xylene, 2-methoxyethanol, reux, 40 h.
the presence of hydrazine monohydrate provided the

selenophene-bridged carbazole dimer 233.3 in 87% yield. The
UVvis spectra of the isophlorins 233.2 and 233.3 were similar
and exhibited absorption bands at 310 and 400 nm, reecting
the nonaromatic character of these macrocycles. Both 233.2
(F = 0.20) and 233.3 exhibited uorescence, although the
quantum yield of the latter system was lower than 0.01, due to
the heavy atom eect of selenium. By treatment with MnO2,
compound 233.3 was converted into the aromatic bis(selenophene) macrocycle 233.4, characterized by a bathochromically shifted porphyrin-like spectrum. Nonaromatic,
mixed-heteroatom systems 234.2 and 234.3 were obtained by
subjecting the thiophenebutadiyne macrocycle 234.1 to
cyclizations with aniline or selenide (Scheme 234).1318 234.3
could be oxidized with MnO2, yielding the aromatic 234.4 with
an optical HOMOLUMO gap of 1.17 eV.
The cyclic tetraindole 235.3 can be regarded as a -extended
porphyrinogen analogue, potentially oxidizable to a planar
porphyrin-like structure (Scheme 235). The synthetic route to
235.3, established by Nakamura, Hiroto, and Shinokubo in
2012, employed the dimerization of borylated bisindole 235.2,
which was synthesized from functionalized aniline 235.1 via a
Stille coupling of carbazole 232.1 and bithiophene 232.2

(Scheme 232).1316 The higher homologues, trithiophenebridged carbazoles 232.5 and 232.6, were prepared in low
yield via Glaser coupling and subsequent annulation with Na2S.
Signicantly better yields were achieved for carbazole dimers
232.7 and 232.8, incorporating both thiophene and bithiophene or trithiophene linkages. The UVvis absorptions of
compounds 232.38 reached up to 455 nm, in line with the
lack of macrocyclic aromaticity of these systems. While they
were not susceptible to MnO2 oxidation, dicarbazoles 232.3,
232.5, 232.7, and 232.8 produced dramatic changes in their
absorption spectra upon treatment with NOSbF6, displaying
NIR absorption bands in the 10002000 nm region. These
spectra apparently corresponded to the formation of radical
cation species, as evidenced by the ESR spectroscopy
measurements.
An attempted synthesis of the furan-bridged carbazole 233.2
via Cu(I)-catalyzed annulation of 228.2 produced the bis(methoxyethoxy) adduct 233.1.1317 Compound 233.1 was
nevertheless transformed into the desired furan derivative,
233.2, using an acid-catalyzed cyclization (Scheme 233).
Moreover, the annulation reaction of 228.2 with selenium in
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Scheme 229. Preparation of Peripherally Ethynylated Carbazole-Based Core-Modied Porphyrinsa
a
Reagents and conditions:1312 (a) NBS, CH2Cl2; (b) tributyl(trimethylsilylethynyl)tin, Pd(PPh3)4, toluene; (c) MnO2, CH2Cl2; (d)
tributyl(triisopropylsilylethynyl)tin, Pd(PPh3)4, toluene; (e) tetrabutylammonium uoride, CH2Cl2; (f) (1) Cu(OAc)2H2O, pyridine, toluene,
(2) Na2S9H2O, p-xylene, 2-methoxyethanol, (3) MnO2, CH2Cl2.
Sonogashira coupling and cycloisomerization (Scheme

235).1319 To prevent potential protodeborylation, 235.2 was
used for the subsequent SuzukiMiyaura without purication.
The oxidized species 235.4 could be obtained from 235.3
either directly or with the intermediacy of the tetrabromo
species 235.5, through the action of dibromine in the presence
of tetrabutylammonium uoride. Macrocycle 235.4 has a
porphyrin-like N4 inner cavity and formed metal complexes
with divalent Cu, Zn, and Ni ion. The free base 235.4 showed
visible absorption extending up to ca. 700 nm, which
underwent considerable red shifts upon metal insertion (up
to ca. 1000 nm for 235.6c). The stepwise method of
synthesizing 235.3 was later elaborated into a general
macrocyclization strategy enabling the construction of mixedheteroatom derivatives 235.710.1320
In the same year, an oxidative coupling route to porphyrinlike cycloindoles was disclosed by Black and co-workers.1321 A
variety of -substituted indoles 236.1ae were employed for
the preparation of 2,7-biindolyls 236.2ad; however, the
coupling was inhibited by strongly electron-withdrawing groups

such as NO2 (Scheme 236). Oxidative coupling of 236.2a in
the presence of p-benzoquinone and acidied dichloromethane
successfully aorded the cyclic tetraindole derivative 236.3a in
50% yield. It was proposed that the head-to-head-coupled
compound 236.3a was preferentially produced due to the
deactivation of the indole C2 position by electron-withdrawing
group at C3. In line with this reasoning, when the bisindole
236.2c was treated with p-benzoquinone under the same
conditions, two macrocyclic products were obtained, the headto-head product 236.3c and the fully symmetrical head-to-tail
236.4c in 18% and 25% yields, respectively.
7.3. Naphtho[2,1,8,7-cdef ]-Fused Porphyrinoids
7.3.1. Arene-Fused Systems. Lateral fusion of appropriately functionalized meso-9-anthryl substituents to the porphyrin ring was explored by Anderson and co-workers. In their
initial work, published in 2008, a single substituent in 237.1 was
oxidatively fused to the macrocycle using DDQ/Sc(OTf)3, to
yield the annulated product 237.2 (Scheme 237).1226 An
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Scheme 230. Synthesis of Fused Porphyrinoids Based on Cyclic Carbazole[2]indolonesa
a
Reagents and conditions:1314 (a) 2,6-diiodo-4-tert-butylaniline, CuI, PdCl2(PPh3)2, K2CO3, THF/Et3N/MeOH, reux, 15 h; (b) InCl3, toluene,
reux, 24 h; (c) (1) trimethylsilylacetylene, CuI, PdCl2(PPh3)2, THF/Et3N, 50 C, 13 h, (2) K2CO3, CH2Cl2/MeOH, rt, 30 min; (d) air, Cu(OAc)2
H2O, pyridine, rt, 18 h; (e) 2,5-bis(tributylstannyl)thiophene, Pd(PPh3)4, toluene, reux, 2 d; (f) MnO2, CH2Cl2, rt; (g) Pd(OAc)2, NaOAc; then
brine, CH2Cl2/MeOH, rt, 24 h.
Scheme 231. Synthesis of a Carbazole-Containing

Porphyrinoida
Scheme 232. Carbazole-Based Expanded

Thiaporphyrinoidsa
Reagents and conditions:1315 (a) Pd(PPh3)4, K2CO3, EtOH, toluene,

85 C; (b) MnO2, CH2Cl2, rt.
isomeric 1-anthryl derivative was converted to the corresponding 237.4 product with a benzo[cd] fusion pattern. The success
of the coupling relied on the presence of activating alkoxy
groups on the anthracene substituent. Porphyrins 237.2 and
237.4 display signicant bathochromic shifts with longestwavelength absorption maxima at 855 and 725 nm, respectively.
Subsequent attempts to prepare bis-anthracene hybrids
revealed the dependence of oxidative coupling on metal
coordination.1227 Treating the zinc complex 237.6 with
Sc(OTf)3/DDQ only gave partially fused porphyrin 237.5,
which could not be oxidized further with an additional amount
of Sc(OTf)3/DDQ. Upon replacing the central ion with Ni(II),
the Sc(OTf)3/DDQ reagent yielded the completely fused
product 237.8. Combined intra- and intermolecular oxidative
coupling of the meso-unsubstituted precursor 237.9 produced
the fused bis-anthracene porphyrin dimer 237.10, characterized
by a NIR absorption at 1495 nm. A porphyrin 237.12 fused to
four anthracenes was eventually reported by the Anderson
group. In their synthesis, all four anthryl groups were coupled
Reagents and conditions:1316 (a) Pd(PPh3)4, toluene, reux, 12 h.
to the Ni(II) porphyrin core in a single-step FeCl 3

oxidation.1228 237.12 showed a very intense Q-band absorption
at 1417 nm ( = 1.2 105 M1 cm1, line width of 284 cm1),
corresponding to an optical band gap of only 0.87 eV.
Functionalized anthracene-fused porphyrins were successfully
used as sensitizers in solar cells exhibiting photocurrent
collection at wavelengths up to ca. 1100 nm, albeit with low
eciency.1322 Photophysical properties of anthracene-fused
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Scheme 235. Cyclic Tetraindoles and Related Systemsa
Scheme 233. Carbazole-Based Porphyrinoids Containing

Selenophene and Furan Ringsa
Reagents and conditions:1317 (a) CuI, 1,10-phenanthroline, KOH, 2methoxyethanol, p-xylene, reux, 16 h; (b) H2SO4, CHCl3, rt, 2 h; (c)
Se, H2NNH2H2O, KOH, DMSO, 100 C, 20 h; (d) MnO2, CH2Cl2,
rt, 3 d.
Scheme 234. Mixed-Heteroatom Carbazole-Based

Porphyrinoidsa
Reagents and conditions:1319 (a) (1) t-BuOK, NMP, rt, (2) 2-bromo4-tert-butyl-6-iodoaniline, PdCl2(PPh3)2, CuI, THFEt3N, rt, (3)
ZnI2, toluene, reux, (4) bis(pinacolato)diboron, [Ir(OMe)cod]2, 4,4di-tert-butyl-2,2-bipyridyl (dtbpy), 60 C; (b) Pd2dba3CHCl3, SPhos,
CsF, Cs2CO3, tolueneDMF, 100 C; (c) (1) TBAF, 0 C, (2) Br2
(10 equiv), THF, 0 C; (d) (1) TBAF, 0 C, (2) Br2 (excess), THF, 0
C; (e) (1) Br2 (excess), THF, rt, (2) NaHSO3H2O; (f) Cu(OAc)2,
CHCl3MeOH, reux for 235.6a; Zn(OAc)2, NaH, DMF, rt for
235.6b; Ni(OAc)24H2O, NaH, DMF, rt for 235.6c.
with DDQ. For easier separation, 238.1ab were reduced to

the [28] state and subsequently reoxidized after purication.
Intramolecular cyclizations were attempted with DDQ/Sc(OTf)3 and FeCl3, but neither experiment was successful. The
bis(AuIII) complex 238.2b, which was more conformationally
rigid than the free base, proved to be more suitable for the
oxidative fusion reaction, producing the fused 238.3b in
acceptable yield. Because of the at and elongated rectangular
conjugated network, 238.3b displayed a remarkably red-shifted
and sharp Q-type band at 1467 nm, seven reversible redox
potentials between 1.02 and 1.76 V implying multicharge
storage ability, and a large TPA cross-section (7600 GM at
1700 nm).
Ecient cyclization of the porphyrin quinodimethane 239.1
was achieved by Wu et al. by using the DDQ/CH3SO3H
oxidant system, aording the target fusion product 239.2
Reagents and conditions:1318 (a) RNH2, CuCl, mesitylene, reux, 1

d; (b) Se, N2H4H2O, KOH, DMSO, 100 C, 20 h; (c) MnO2,
CH2Cl2, rt, 3 d.
systems were investigated theoretically using DFT and coupledcluster methods.1323,1324

Osuka et al. reported the synthesis of 238.3, a [26]hexaphyrin fused to two anthracenes (Scheme 238).1325
Anthryl-substituted macrocycles 238.1ab were prepared by
the condensation of tripyrrane and 9-formylanthracene in the
presence of methanesulfonic acid at 0 C, followed by oxidation
EZ
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existed as the triplet biradical, conrmed by ESR measurements, and its UVvisNIR spectra showed a broad redshifted absorption extending beyond 1200 nm. DFT calculations (UB3LYP/6-31G*) suggested that porphyrin 241.2 has
an open-shell triplet ground state (s2 = 2.1194) with a
singlettriplet energy gap (EST) of +6.98 kcal mol1. The
molecular orbital (MO) characteristics and spin density maps
indicated a nondisjoint character of nonbonding orbitals and
negligible spin density on the Ni atom. A closed-shell ground
state was identied for compound 241.1 on the basis of the
sharp NMR spectrum observed even at elevated temperatures.
This observation was supported by DFT calculations, which
indicated a small singlet biradical contribution (y = 0.06; EST
= 4.28 kcal mol1).
A dierent type of phenalene fusion was explored reported in
2016 by Thompson et al.1329 Starting with the bis(2,3-dihydro1H-phenalen-6-yl)-substituted porphyrin 241.8, they obtained
the fully conjugated system 241.11 in a two-step synthesis,
consisting of FeIII-mediated oxidative coupling of one
substituent followed by thermal annulationdehydrogenation.
241.11 was shown to be a diamagnetic system with a strongly
red-shifted absorption spectrum (max = 796 nm) and weak
NIR emission (maxem = 835 nm, F = 0.003). A partial chargetransfer character was ascribed to the HOMOLUMO
transition on the basis of the partially disjoint spatial
distribution of frontier orbitals. Broken-symmetry DFT
calculations indicated an insignicant biradicaloid character.
7.3.2. Porphyrin Tapes. Conjugated porphyrin oligomers,
in which consecutive macrocyclic units are triply linked via
adjacent , meso, and positions (porphyrin tapes), have been
the subject of intense research because of their unique
electronic features and potential use as components for organic
electronics with nanometer-scale dimensions.1330 A feasible and
general synthesis of these systems, known as oxidative doublering closure (ODRC1331), was developed by Osuka and coworkers in 2000,1332 elaborating on the earlier discovery of
direct mesomeso oxidative coupling.1333 In the original work,
diporphyrin Cu complex 242.1 was treated with 2 equiv of
tris(4-bromophenyl)aminium hexachloroantimonate (BAHA)
in C6F6 at room temperature for 2 days, to provide triply linked
dimers 242.3ab in 62% and 6% yields, respectively (Scheme
242).1332 The oxidation of 242.1 carried out in CHCl3 instead
of C6F6 led to extensive -chlorination, indicating that the
abstraction of chlorine was solvent-dependent. Triporphyrin
242.2 was oxidized in a similar manner to give the fused trimer
242.4 in a 33% yield along with the recovered starting material
(30%).
In contrast to singly linked oligomers 242.1 and 242.2, in
which pairs of adjacent porphyrin subunits are perpendicular to
one another, the triply linked arrays 242.3 and 242.4 contain a
contiguous, completely planarized -conjugated system.
Oligoporphyrins 242.3 and 242.4 showed red-shifted UV
visNIR spectra with absorption maxima at 411, 576, and 996
nm and at 413, 657, and 1251 nm, respectively. The eect of
the central metal on the electronic interaction was preliminarily
examined by comparing CuII-diporphyrin 242.3a and ZnIIdiporphyrin 242.3c. The most red-shifted Q-band is observed
at 1068 nm in 242.3c, being red-shifted by 72 nm more than
242.3a. The one-electron oxidation potentials of 242.3a and 3c
are 0.39 and 0.11 V, respectively. Diverse analogues of 242.3,
containing mixed substituents or metal ions, were subsequently
reported by several groups.13341337 The majority of these
systems contained meso-aryl groups, which were introduced to
Scheme 236. Synthesis of Macrocyclic Tetraindoles via

Oxidative Coupling Reactionsa
Reagents and conditions:1321 (a) SnCl4, CH2Cl2, MeNO2, MeCN,

reux, 12 h; (b) HCl, p-benzoquinone, CH2Cl2, rt, 3 h.
(Scheme 239).1326 Compound 239.1 showed two distinct

absorption bands at 450 and 635 nm in CH2Cl2, while 239.2
displayed a red-shifted absorption spectrum with two major
bands at 533 and 780 nm together with two weak bands at 669
and 897 nm due to extended -conjugation. The corresponding
optical energy gaps were determined to be 1.69 and 1.33 eV for
239.1 and 239.2, respectively, from the onset of the lowest
energy absorption band. An unusual negative shift of the rst
oxidation potential was observed for the highly contorted
molecule 239.1.
Similarly designed, nonquinoidal BODIPYporphyrin hybrids were subsequently reported by the Wu group.1327 FeCl3
was utilized to promote intramolecular ring fusion of 240.1
yielding the fully condensed product 240.2 (Scheme 240).
Further extension of the -conjugation length was achieved by
fusing two BODIPY subunits to the porphyrin ring. Complete
oxidation of 240.3 to 240.4 required forceful conditions,
aording the product in only 15% yield. Compounds 240.2 and
240.4 showed intense NIR absorption maxima at 890 and 1040
nm, respectively, and excellent photostability. Wide spectral
coverage, as well as the amphoteric redox behavior of these
systems, indicated their potential use in photovoltaic devices.
Phenalenylporphyrin hybrids 241.12 were designed by
the Wu group as potentially stable biradicaloid systems.1328 The
fusion of one phenalenyl unit to the porphyrin core was
successfully achieved by an intramolecular FriedelCrafts
alkylation of 241.3 promoted by BF3Et2O, aording the
dihydro precursor 241.4 in 67% yield (Scheme 241). Oxidative
dehydrogenation of 241.4 with N-iodosuccinimide (NIS)
resulted in the desired -extended porphyrin 241.1. A similar
strategy was used for the synthesis of 241.2, except that in the
nal step, NIS was replaced by p-chloranil as the dehydrogenative agent. Porphyrin 241.2 could not be isolated in pure form
because of its air-sensitivity. Upon exposure to air for 3 h, it was
transformed into two dioxo-porphyrin isomers 241.7ab.
Compound 241.1 showed higher stability but decomposed in
protic solvents during crystallization. The unstable 241.2
FA
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Scheme 237. Synthesis of Anthracene-Fused Porphyrinsa
Reagents and conditions: (a)1226 Sc(OTf)3, DDQ, DCM, 20 C; (b) Sc(OTf)3, DDQ, DCM, 40 C; (c)1227 Sc(OTf)3/DDQ; (d) (1) TFA, DCM,
(2) Ni(acac)2, xylene, 130 C; (e) (1) FeCl3, CH3NO2, DCM, (2) FeCl3, AgOTf, CH3NO2, toluene; (f) Sc(OTf)3, DDQ, DCM; (g)1228 FeCl3,
DCM.
a
Scheme 238. Synthesis of a Hexaphyrin Fused with Two Anthracene Moietiesa
Reagents and conditions:1325 (a) Na[AuCl4]2H2O, NaOAc, Ag2CO3, CH2Cl2/MeOH; (b) DDQ, Sc(OTf)3.
suppress -stacking of the extended conjugated surfaces. For
absorbers and emitters with very large TPA cross sections,13431345 and as semiconducting liquid crystals.13461348
Direct oxidative coupling of 5,10,15-triaryl metalloporphyrins
containing dierent metals (243.1a and 214.1b,c,e, Scheme
243) using the DDQSc(OTf)3 couple revealed strong metalion-dependent regioselectivity.1349 Oxidation of the zinc
complex 214.1c yielded exclusively the triply linked derivative
comparison, the n-hexyl-substituted dimer 242.5, obtained

using the DDQ/Sc(OTf)3 reagent, displayed strong aggregation in noncoordinating solvents.1338 Functionalized triply
linked dimeric and trimeric oligomers were explored as
elements of covalent supramolecular assemblies,13391342 NIR
FB
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bearing electron-rich 3,5-di-tert-butylphenyl groups.1350 PIFA

oxidation was instrumental in the synthesis of 244.7, a
derivative containing six thioglucose units appended to
peruoroaryl substituents, which could not be obtained with
the DDQ/Sc(OTf)3 oxidant.1354 The amphiphilic compound
244.7, which is chemically and photochemically stable, was
taken up by breast cancer cells and caused cell death upon
exposure to light. Further photophysical studies of 244.7
revealed absorption bands in the near IR region (the lowest
energy at 1090 nm in DMSO), and photosensitized formation
of singlet oxygen with high quantum yield (0.78 0.03 in
DMSO).
Anderson, Armaroli, et al. investigated a deuterated dimeric
porphyrin array 245.1 to test whether deuteration inuences
the rate of nonradiative S1S0 deactivation.1355 Their synthetic
strategy involved initial deuteration of dipyrromethane 245.2 in
the two-phase D2OCH2Cl2 system (Scheme 245). In the
target 245.1, obtained from 245.2 using previously reported
methods, the -pyrrolic positions were approximately 91%
deuterium-enriched and the aryl substituents were also partially
deuterated. The absorption spectra for both the deuterated and
the nondeuterated dimers were identical, indicating that the
electronic structure was not aected by deuteration. The
uorescence quantum yield was completely unaected by
deuteration (fD/fH = 1.00 0.05), demonstrating that CH
vibrations do not contribute to the radiationless deactivation of
the S1 state (i.e., internal conversion). It was proposed that a
specic deactivation pathway was active via an accessible
intersection of the S1 and S0 potential energy surfaces.
Osuka and co-workers reported that triply linked diporphyrin
246.1 underwent site-selective cycloaddition reactions with
thermally generated o-xylylene 246.2 to provide a mixture of
[4+2] and [4+4] cycloadducts, 246.3 and 246.4 (Scheme
246).1356 Oxidation of the latter product with DDQ provided a
triply linked diporphyrin 246.5 fused with a benzocyclooctatriene moiety. Further dehydrogenation of 246.5, aimed at
obtaining the corresponding cyclooctatetraene-fused derivative,
was ineective under a variety of conditions. The absorption
spectrum of 246.5 was quite similar to that of the parent 246.1,
with red-shifted Q-like bands (above 1000 nm). In contrast, the
absorption spectra of 246.3 and 246.4 were ill-dened, and
blue-shifted, exhibiting the lowest-energy bands at 820 and 729
nm, respectively.
In related work from the Osuka group, 246.1ab were
shown to undergo a rare [3+4] cycloaddition reaction with
azomethine ylide 246.6, prepared in situ from sarcosine and
para-formaldehyde.1357 The resulting bischlorin adduct 246.7a
had a low oxidation potential of only 0.05 V and proved to be
unstable in air, gradually reverting to the parent dimer 246.1. In
contrast, the Ni complex 246.7b was thermally stable, and it
was possible to obtain it in a higher yield (42%). Attempted
syntheses of the corresponding bisporphyrins via oxidation of
246.7a and 246.7b with DDQ, chloranil, and manganese
dioxide failed, producing instead the parent dimers 246.1. The
absorption spectral features of 246.7a and 246.7b were similar
to those of the 246.3 and 246.4 bischlorins,1356 displaying a
split Soret-like band and complicated Q-like bands.
Triply fused porphyrin dimers were subjected to a range of
peripheral extensions involving carbo- and heterocyclic units.
Osuka, Kim, et al. employed the retro-DielsAlder strategy in
the synthesis of the tetrabenzo-fused triply linked diporphyrin
247.5 (Scheme 247).1358 Initially, bicyclo[2.2.2]-octadienecondensed porphyrin 247.1 was obtained by TFA-catalyzed
Scheme 239. Synthesis of Fused Quinoidal Porphyrin 239.2a
Reagents and conditions:1326 (a) DDQ, MeSO3H, CH2Cl2, rt, 20

min.
Scheme 240. Synthesis of BODIPY-Fused Porphyrinsa
Reagents and conditions:1327 (a) FeCl3, MeNO2, CH2Cl2, rt; (b)

FeCl3, MeNO2, CH2Cl2, reux.
242.3c in 86% yield, whereas 214.1b selectively produced the

meso doubly linked dimer 214.2b in 74% yield. Both types
of coupling product were produced simultaneously in
oxidations of Cu and Ni complexes. The observed coupling
regioselectivities are analogous to those found for oxidation
with BAHA. Oxidation of triarylmetalloporphyrins bearing a
sterically hindered phenolic substituent at position R 1
produced, in addition to bisporphyrins, also quinoidal
monomers, such as 243.4.
As shown above, DDQ/Sc(OTf)3 is a particularly versatile
reagent for the synthesis of triply linked dimers and works even
with relatively electron-poor systems, for example, containing
peruorophenyl meso substituents.1336 However, the coupling
can also be eected with a range of other oxidants such as
PIFA, which enables precise control of oxidation stoichiometry,1337,1350 PIFABF3Et2O,1351 Cu(II) salts,1352 and Fe(OTf)3.1353 In the latter case, coupling regioselectivity was
shown to depend on the oxidation potential, with the lowpotential reactants favoring triply linked products (Scheme
244). With PIFA, a regioselectivity dependent on mesosubstituents was achieved in the synthesis of 244.5, in which
the ODRC reaction occurred only between porphyrin subunits
FC
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Scheme 241. Synthesis of Phenalenyl-Fused Porphyrinsa
Reagents and conditions: (a)1328 KOAc, CH3CN, THF, reux, 1 day; (b)1328 LiOH2H2O, dioxane, H2O, reux, 2 days; (c)1328 (1) oxalyl chloride,
DMSO, DCM, Et3N, (2) Ni(acac)2, toluene, reux, 24 h; (d)1328 (1) mesitylmagnesium bromide, THF, rt, 24 h, (2) excess BF3Et2O, DCM, 10 min;
(e)1328 NIS, DCM; (f)1328 p-chloranil, DCM; (g)1328 air; (h)1329 FeCl3, CH2Cl2; (i)1329 500 C.
Scheme 242. Synthesis of Completely Fused Diporphyrins and Triporphyrina
Reagents and conditions:1332 (a) BAHA, C6F6, 2 days.
the tetrabenzo-fused compound 247.4. The meso-bonded

diporphyrin 247.4 was oxidized with the DDQSc(OTf)3
reagent system, yielding the 247.5 target in good yield. An
condensation followed by oxidation. In the next step, 247.1 was

converted into 247.2 via AgPF6-promoted mesomeso
coupling. Heating to 210 C under reduced pressure provided
FD
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Scheme 243. Oxidative Coupling of 5,10,15-Triarylporphyrinsa
Reagent and conditions: (a)1349 DDQ, Sc(OTf)3, toluene, 50 C.
Scheme 244. Oxidative Coupling of Porphyrins with PIFA and Fe(OTf)3a
Reagents and conditions: (a)1353 5.0 equiv of Fe(OTf)3, CH2Cl2/CH3NO2; (b)1350 0.5 equiv of PIFA, CH2Cl2; (c) 1.5 equiv of PIFA, CH2Cl2.
Scheme 245. Synthesis of a Deuterated Conjugated Porphyrin Dimera
a
Reagents and conditions:1355 (a) d-TFA, D2O, CH2Cl2; (b) (1) 3,5-di-tert-butylbenzaldehyde, TFA, CH2Cl2, (2) DDQ; (c) Ni(OAc)2, DMF,
reux; (d) (1) 3,5-di-tert-butylphenyllithium, THF, 0 C to rt, (2) D2O, (3) DDQ; (e) (1) D2SO4, CH2Cl2, (2) Zn(OAc)22H2O, MeOH, CH2Cl2;
(f) Sc(OTf)3, DDQ, PhMe.
alternative route, involving initial ODRC to produce 247.3, was

less ecient because of the low solubility of the latter
intermediate. Compound 247.5 exhibits a perturbed absorption
spectrum and a large two-photon absorption cross section

(15 400 GM at 1260 nm).
FE
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Scheme 246. Bay-Region Cycloadditions to a Triply Linked Diporphyrina
a
Reagents and conditions: (a)1356 benzosultine (7 equiv, gradual addition), toluene, reux; (b) DDQ, CHCl3; (c)1357 sarcosine, paraformaldehyde,
toluene, reux; (d) oxidant (DDQ, chloranil, or MnO2).
Scheme 247. Synthesis of a Benzo-Fused Porphyrin Dimera
Reagent and conditions:1358 (a) AgPF6CHCl3; (b) DDQSc(OTf)3; (c) 210 C, 0.1 mmHg for 30 min.
annulated perylene, 249.3ab showed a very intense

absorption beyond 1250 nm. The maximum TPA cross-section
values ((2)) of 249.2a and 249.2b were measured at 2100 nm
as 890 and 1100 GM, respectively. Fused compounds 249.3a
and 249.3b exhibited larger (2) values of 1400 GM (at 2200
nm) and 1500 GM (at 2400 nm), respectively.
In 2001, the Osuka group showed that triply linked
porphyrin n-mers with n = 212 (250.2n) could be eciently
obtained in the oxidative double-ring closure (ODRC) reaction
of mesomeso-linked porphyrin oligomers (Scheme 250).1331
The ODRC reaction was conducted by reuxing a toluene
solution of 250.1n in the presence of DDQ/Sc(OTf)3,
providing yields from 60% to 91%. The ODRC results in a
complete attening of the oligomer chains, which was visualized
using STM for dierently substituted analogues of 250.16
and 250.26 adsorbed on Cu(100).1361 Fused tape-shaped
porphyrin arrays 250.2n display spectacular red shifts of their
absorption bands, in comparison with their singly linked
precursors. The wavelength of the lowest-energy band
increased linearly with the oligomer length, each porphyrin
subunit introducing an average red shift of 175 nm.
Consequently, these absorptions spanned a remarkable range
from 9400 cm1 for 250.22 to 3500 cm1 for 250.212. In
fact, for the longest oligomers, the low-energy absorptions
In 2010, the Thompson group described the synthesis and

properties of -meso- bonded porphyrin dimers fused with
two pyrene units (Scheme 248).1232 The meso-pyrenesubstituted intermediate 248.3 was obtained via oxidative
cyclodehydrogenation of 248.2. Fusion of the pyrene
substituents did not occur under the latter conditions and
was therefore eected by means of FeCl3 oxidation, yielding
248.4a. The position of the lowest-energy Q-band varied
considerably with metal coordination, ranging from 1269 nm in
the free base, through 1323 nm in the Zn complex 248.4b, to
1459 nm in the Pb complex 248.4c, the latter value being
comparable with that of the related bis-anthracene diporphyrin
(237.4, vide supra). Compound 248.4b showed promising
properties for use in NIR photodetector applications.1359
Porphyrin dimers fused with N-annulated perylene (NAP)
units were reported by Wu, Kim, and co-workers1360 (for other
NAPporphyrin hybrids, see Scheme 52, section 3.2).
Oxidative couplings and cyclodehydrogenations of 249.1 were
attempted using PIFA and Sc(OTf)3/DDQ (Scheme 249). By
carefully controlling the reaction temperature and amount of
oxidant, both the partially fused 249.2 and the fully fused 249.3
porphyrin tapes could be obtained in reasonable yields. Because
the fusion direction coincides with the S0S1 transition
moment axes of both the fused porphyrin dimer and the NFF
Chemical Reviews
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Scheme 248. Fully Fused PyreneDiporphyrin Hybridsa
Scheme 250. Synthesis of Fully Conjugated Porphyrin

Tapesa
Reagents and conditions:1331 (a) DDQ, Sc(OTf)3, toluene, reux.
to enclose each porphyrin subunit.1362 This modication

resulted in the suppression of stacking and in improved
chemical stabilities of the longest tapes.
A considerable amount of theoretical and experimental work
has been devoted to the study of electronic structure of
porphyrin tapes. Individual porphyrin macrocycles in fully
conjugated oligoporphyrins exhibit dierent degrees of macrocyclic aromaticity, and a theoretical method for estimating these
properties was proposed by Aihara and Makino.1363 Kims
group explored the role of the naphthalene junctions in the
electronic delocalization in linear and branched Zn porphyrin
tapes.1364 It was proposed on the basis of GIAO and AICD
calculations that the unique -conjugation behavior of triply
linked tapes is induced by their intrinsic molecular orbital
interactions and subsequently by antiaromatic naphthalene and
COT junctions, in one- and two-dimensional systems,
respectively. Consequently, linear tapes were viewed as a
superposition of alternating aromatic (porphyrin-centered) and
antiaromatic (naphthalene-centered) units. The structural
deformation by triple linkages was observed to have a negative
a
Reagents and conditions:1232 (a) 4,4,5,5-tetramethyl-2-(pyren-1-yl)1,3,2-dioxaborolane, [Pd(PPh3)4], Cs2CO3, toluene, 110 C; (b)
Sc(OTf)3, DDQ, toluene, 110 C; (c) FeCl3, CH2Cl2, 20 C, then aq
HCl (M = 2H); (d) Zn(OAc)2, MeOH, CH2Cl2; (e) Pb(OAc)2,
pyridine, CH2Cl2.
overlapped with the vibrational part of the spectrum, leading to

a decrease of intensity of CH stretching vibrations. The oneelectron oxidation potentials also decreased progressively upon
the increase in the number of porphyrins unit. Longer arrays
(most notably 250.212) exhibited low solubility due to
aggregation. This problem was partly alleviated in later work, in
which double 1,10-dioxydecamethylene straps were introduced
Scheme 249. Oxidative Fusion of meso-Substituted Porphyrina
Reagents and conditions:1360 (a) 5 equiv of Sc(OTf)3, DDQ, toluene, 90 C; (b) 5 equiv of Sc(OTf)3, DDQ, toluene, 50 C.
FG
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Scheme 251. -Extended Porphyrin Tapes with Mixed Substitutiona
Reagents and conditions:1373 (a) (1) Pd2(dba)3, tri-2-furylphosphine, Cs2CO3, THF, DMF, H2O, (2) Zn(OAc)2, MeOH, CHCl3; (b) AgPF6,
CH3CN, CHCl3, rt, 12 h; (c) AgPF6, DMA, CH3CN, CHCl3, reux, 72 h; (d) DDQ, Sc(OTf)3, toluene, 80 C, 2 h.
eect on the electronic delocalization between the inner and

outer porphyrin units.
Porphyrin tapes exhibited a rapid formation of the lowest
excited states and an acceleration of relaxation dynamics of the
lowest excited state from 4.5 ps for the dimer up to 0.3 ps
for the hexamer.1365 Further examination of longer arrays (up
to 8-mer) showed that excited-state dynamics changed
systematically as the number of porphyrin moieties increased,
revealing the occurrence of two simultaneous relaxation
processes.1366 The electronic transition process, for which the
recovery time constant becomes shorter as the number of the
porphyrin units increases, competes with vibrational relaxation
processes, strongly aected by structural and environmental
inhomogeneities. TPA cross-section values measured in
solution for triply linked Zn oligomers at 1200 nm showed a
continuous increase as the array became longer (11 900,
33 100, and 93 600 GM for the dimer, trimer, and tetramer,
respectively).1367 Second hyperpolarizabilities () of doubly
and triply linked porphyrin tapes were evaluated using the
PariserParrPople theory.1368 It was found that triply linked
arrays exhibit remarkable evolution of /n with the increase in
the number of units, and the is 3 orders of magnitude larger
than in butadiyne arrays in the limit of innite n. Magnetic
circular dichroism (MCD) spectra of doubly and triply linked
fused bisporphyrins and triply linked higher oligomers (up to
four units) were measured, showing no dependence on the
central metal atom or solvent.1369 Observed spectral patterns
were considered to result from the strong perturbation of the
porphyrin skeleton caused by direct linkages between
chromophores. It was also demonstrated that the MOs of
the investigated arrays could be constructed as a linear
combination of the constituent monomeric MOs, and that

the eect of lowering the symmetry was always larger on the
LUMO than on the HOMO orbital.
Electrical conduction measurements were performed on a
singly linked oligomer consisting of 48 porphyrin units, which
showed a diode-like behavior, and on an 8-membered triply
linked array.1370 IV curves recorded for the latter system
showed that the stronger -electron conjugation led to higher
conductivity and a smaller band gap. Measurements of electrical
transport through singly and triply linked thiol-terminated
porphyrin arrays showed a slower than expected decrease of
conductance with the molecular length.1371 Using the I(s)
implementation of the STM technique, 4-pyridyl-terminated
triply linked porphyrin dimer and trimer were shown to have
higher conductance in the Au|oligoporphyrin|Au junctions than
their singly linked and butadiyne-bridged analogues.1372
The synthesis of long porphyrin tapes is made dicult by
limited length-selectivity of porphyrin mesomeso couplings,
aggregation of triply linked tapes, and the consequent solubility
problems. Osuka and co-workers addressed these issues by
devising a stepwise oligomerization protocol and introduction
of a mixed substitution pattern (Scheme 251).1373 The
synthesis began with the SuzukiMiyaura coupling of dierently substituted monomers 251.1 and 251.2, followed by
zinc(II) insertion, which produced the mesomeso-linked
hybrid diporphyrin 251.32. In the next step, 251.32
underwent an Ag-promoted oxidation coupling to produce
longer arrays 251.34 and 251.36. The presence of bulky
groups (R1) on one of the porphyrin units in 251.32 makes
the coupling highly regioselective, yielding only head-to-tail
coupled products. By using the Ag oxidant under more forceful
FH
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The ODRC strategy, used to synthesize triply linked

oligomers, was also employed by Osuka, Kobayashi, Kim, et
al. for the synthesis of the tetrameric porphyrin sheet 252.1
(Scheme 252).1375 It was obtained by direct DDQ/Sc(OTf)3
conditions, 251.34 was oligomerized further, to yield singly

linked chains 251.3n with lengths up to n = 24. The
transformation of available 251.3n oligomers into the
corresponding porphyrin tapes 251.4n was achieved with
the DDQ/Sc(OTf)3 reagent system in good yields (3868%).
The remarkable length-dependent red shift of the lowestenergy Q-band was again observed in the 251.4n series, but it
was found to become saturated at n = 16. The eective
conjugation length of porphyrin tapes was therefore estimated
to be around 1416 units, corresponding to the physical length
reaching about 12 nm.
In 2014, temperature-induced covalent dehydrogenative
coupling between unsubstituted free-base porphine molecules
was reported by Auwarter et al. to yield fused dimers and larger
oligomers (exceeding 90 porphine units) directly on a Ag(111)
support under ultrahigh-vacuum conditions.1374 The reaction
provides simultaneously three fusion motifs: (1) , meso
meso, characteristic of porphyrin tapes, (2) meso,
meso, and (3) , meso (Figure 5). The percentage of the
triply fused motif 1 decreased with increasing substrate
temperature from 81 5% (TS = 533 K) to 67 6% (TS =
613 K). Binding motif 2 showed no pronounced temperature
dependence, while motif 3 became more likely with increasing
temperature.
Scheme 252. Synthesis of Porphyrin Sheetsa
Reagents and conditions: (a)1375 DDQ, Sc(OTf), toluene, 55 C;

(b)1377 TFA, H2SO4, CHCl3, 0 C to rt; (c) Cu(OAc)2 in MeOH,
CHCl3, reux.
a
oxidation of the cyclotetrameric singly linked porphyrin array

252.2, which was synthesized in a stepwise manner from the
252.3 building block utilizing a previously reported procedure.1376 A more convenient, although lower-yielding, synthesis
of 252.1 was subsequently reported, involving noncyclic
angularly meso-linked tetramers.1377 UVvis absorption measurements showed considerably broadened absorption bands,
with the most red-shifted region occurring between 1000 and
1500 nm. In comparison to the one-dimensional tetrameric
porphyrin tape, 252.1 exhibited a slightly longer-lived S1-state
(1.1 ps) and a smaller TPA cross section (2750 GM). The
252.1 sheet formed stable 1:2 and 2:4 complexes with specially
designed bisimidazolyl1375 and bispyridyl1378 derivatives, which
acted as bidentate apical ligands coordinating to the Zn centers.
Chemical shifts observed for the bound ligands and NICS
calculations were used to demonstrate a considerable paratropic
ring-current eect around the planar cyclooctatetraene ring
embedded in the center of 252.1.1375,1378 The 1H NMR
spectrum of the free base 252.4, obtained by demetalation of
252.1, showed that the porphyrin rings exhibit no diatropic ring
currents and that the NH tautomerism is completely frozen.1377
Tetranuclear Cu(II) complex 252.5 exhibited antiferromagnetic
interaction among the CuII ions with J = 1.16 cm1.
First-principles calculations were performed to investigate
the electron spin-polarization and magnetic ordering in innite
2D polyporphyrin sheets based on the motif found in
252.1.1379 The magnetic coupling between the local magnetic
moments in the free base sheet was very weak, exhibiting
paramagnetic features. The chromium complex array had a
ferromagnetic ground state, while other transition metal
Figure 5. STM observations of porphine homocoupling. (a) Random

distribution of individual porphine molecules on Ag(111) after
deposition at a sample temperature TS of 345 K (13.0 19.8 nm2,
0.8 V, 0.2 nA). (b) Overview image after annealing a porphine
multilayer, grown at room temperature, to TS = 573 K. The colored
circles highlight distinct species: monomer (blue), dimer (green), and
trimer (yellow). The bright features (dashed circle) are assigned to
porphines interacting with Ag adatoms (28.0 19.8 nm2, 0.2 V, 0.1
nA). (c) Porphine monomer with structural model and rst symmetry
axis (red dotted line). Directions of the Ag(111) substrate are
indicated in white. (df) Three dierent binding motifs for oligomers
with corresponding structural models and symmetry axes (2.5 2.5
nm2, 0.15 V, 0.12 nA). C, N, and H atoms are indicated in cyan, blue,
and white, respectively. (d) Binding motif 1 of triply fused dimer: ,
mesomeso, (positions are labeled and marked by arrows in (c)).
(e) Binding motif 2 of doubly fused dimer: meso-, -meso. (f)
Binding motif 3: , meso-. Adapted with permission from ref
1374. Copyright 2014 American Chemical Society.
FI
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Scheme 253. Synthesis of Two-Dimensionally Extended Porphyrin Tapesa
Reagents and conditions:1380 (a) DDQ, Sc(OTf)3, toluene.
Scheme 254. Synthesis of Fused Hybrid PorphyrinHexaphyrin Tapesa
Reagents and conditions: (a)1381 BF3Et2O, CH2Cl2, 30 min, rt, then DDQ, 1 h; (b)1381 DDQ, Sc(OTf)3, 80 C, 5 h; (c)1381 NaBH4; (d)1381
MnO2; (e)1385 DDQ, Sc(OTf)3, 80 C, toluene.
a
Hybrid porphyrinhexaphyrin tapes were synthesized by

applying the ODRC reaction to mixed meso-linked oligomers
(Scheme 254). Dimer 254.3 was obtained in a crosscondensation of meso-porphyrinyl-dipyrromethane 254.1,
dipyrromethane 254.2, and peruorobenzaldehyde, to be
converted into the fused target 254.4 using the usual DDQ/
Sc(OTf)3 oxidation.1381 The NIR spectrum of 254.4 shows the
lowest-energy maximum at 1333 nm with a tail reaching to ca.
1600 nm. In analogy to nonfused hexaphyrins,1382,1383 the
[26]hexaphyrin unit in 254.4 could be quantitatively reduced
with NaBH4 to yield the [28]hexaphyrin tape 254.5. The
complexes showed either antiferromagnetic or paramagnetic

ground states.
Two structurally related angular porphyrin tapes, the Lshaped trimer 253.1 and T-shaped tetramer 253.2, were
elaborated by Osuka and co-workers using the ODRC strategy
(Scheme 253).1380 The use of nonyl substituents was dictated
by the steric demands of the branched tape design. Branching
of the fused framework in 253.1 and 253.2 resulted in a marked
decrease of TPA cross sections relative to their linearly fused
analogues.
FJ
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Scheme 255. Synthesis of DehydropurpurinPorphyrin Dyads and Dehydropurpurin Dimersa
Reagents and conditions:1386,1387 (a) AgPF6, CHCl3, rt, 6 h; (b) 1,4-diphenylbutadiyne, (o-Tol)3P, [Pd2(dba)3], NEt3, toluene, 110 C; (c) mesobromoporphyrin (ca. 3.5 equiv), (o-Tol)3P (2 equiv), [Pd2(dba)3] (50 mol %), NEt3 (5 equiv), DMF, 110 C; (d) meso-bromoporphyrin (5 equiv),
(o-Tol)3P (2 equiv), [Pd2(dba)3] (50 mol %), NEt3 (5 equiv), DMF, 110 C; (e) NBS, pyridine, CHCl3/EtOH, 0 C (for a); NBS, pyridine,
CHCl3/EtOH, 0 C, then Zn(OAc)22H2O, CH2Cl2/MeOH (for c).
(5,15-diaryl-10-phenylethynylporphyrinato)zinc(II) complexes
255.1 gave directly linked 12,13-dehydropurpurinporphyrin
dyads 255.2ab, and no product of meso-coupling was
observed (Scheme 255).1386 The direct connection between
the two macrocycles led to a strong electronic interaction and
caused broadening of absorption bands. Compound 255.2a
possessed a split Soret band with maxima at 421 and 471 nm,
while a broad Q-like band was observed at 645 nm. In
subsequent work, a Pd-catalyzed [3+2] annulation of
bromoporphyrin 255.3 with 1,4-diphenylbutadiyne gave
alkynyl-7,8-dehydropurpurins 255.4 and 255.5.1387 In the
next step, the [3+2] annulation of 255.5 with 255.3 was
achieved under similar conditions, providing dimers 255.6 and
255.7. The reaction of 255.3 and 255.4 was also attempted,
furnishing 255.8 with a 42% recovery of 255.4. The UVvis
NIR absorption spectra of 255.6 contained well-dened nearinfrared bands at 939 and 1056 nm, in contrast to 255.7 and
255.8, which have extremely broad bands reaching to ca. 1050
nm. The electrochemical HOMOLUMO gap of 255.6 was
1.26 eV, distinctly smaller than those of dimers 255.7 and
255.8 (1.52 and 1.62 eV, respectively). Additionally, 255.6
reacted with N-bromosuccinimide to produce -to- vinylenebridged porphyrin dimers anti- and syn-255.9.
electronic spectrum of 254.5 is qualitatively similar to that of

254.4, although it reveals a blue shift in the NIR range as well
as marked dependence on solvent polarity, possibly associated
with a solvent-induced conformational change. In opposition to
the optical parameters, the electrochemical HOMOLUMO
gaps were determined to be 0.87 and 0.63 eV for 254.4 and
254.5, respectively. This apparent discrepancy was explained by
assuming that the HOMOLUMO transition in the antiaromatic 254.5 is dipole-forbidden. In subsequent work from
the Osuka group, bis-rhodium(I) complexes of 254.4 and
254.5 were reported.1384 The methodology used to make 254.4
was extended to synthesize the hybrid tapes 254.7ab,
consisting of two porphyrin and hexaphyrin moieties.1385
254.7a and 254.7b showed remarkably shifted Q-bands (at
1657 and 1912 nm, respectively), six to seven reversible
electrochemical events, and narrow HOMOLUMO band gaps
(0.52 and 0.67 eV for 254.7a and 254.7b, respectively).
7.4. [cd]-Fused Porphyrinoids with 5- and 7-Membered
Rings
7.4.1. Dehydropurpurins. The Ag-mediated oxidations of

meso,-free porphyrins generally produce doubly and triply
linked porphyrin tapes described above. However, it was found
by the Osuka group that an AgPF6-promoted oxidation of
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Scheme 256. Pd-Catalyzed [3+2] Annulation of Porphyrins with Alkynesa
Reagents and conditions:1388 (a) (o-Tol)3P (20 mol %), [Pd2(dba)3] (5 mol %), R1CCR1 (1.5 equiv), Cy2NMe, toluene, reux, 24 h; (b) air and
light, 3 h.
In Pd-catalyzed [3+2] alkyne annulations, developed by

Osuka, Shinokubo, et al., meso-bromo metalloporphyrins
256.1ac reacted with a variety of nonterminal alkynes,
yielding 7,8-dehydropurpurin derivatives 256.2aj in very
good yields (6987%, Scheme 256).1388 The reaction
proceeded cleanly without byproducts, other than the
debrominated porphyrin. Cyclic voltammetry measurements
showed a small separation between the rst oxidation and the
rst reduction potential (E = 1.66 V) for 256.2a relative to
that of 5,15-bis(3,5-di-tert-butylphenyl)porphyrin nickel(II)
(E = 2.29 V). The UVvis absorption spectra of these
dehydropurpurins reached into the near-infrared. Quantitative
conversion of compound 256.2h into the meso,-dibenzoylporphyrin 256.3h was observed after exposure of the solution to
air under ambient light. A related annulation, involving the use
of silylacetylenes, was later developed by the Osuka group,
providing access to cyclopentadiene-unsubstituted dehydropurpurin derivatives.1389
7.4.2. Indeno[1,2,3-cd]porphyrins. As discussed in the
preceding section, treatment of metal complexes of 2-formylmeso-tetraarylporphyrins with strong acids results in an
intramolecular cyclization leading to naphthoporphyrin derivatives. In 1994, Dolphin et al. observed that in the case of
porphyrins bearing electron-donating m-methoxy groups on the
meso-aryl substituents, an additional cyclization occurs at the
same pyrrole ring, producing cyclopenta-fused products C60.1
and C60.2 (or C60.3) in a nonregioselective manner (Chart
60).1292 Absorption spectra of these fused compounds were
measured, and the most red-shifted band was observed at 768
nm for C60.1b.
In 2004, Boyle and co-workers reported Pd-catalyzed ring
closure reactions of iodinated, meso-arylporphyrins, providing
access to indeno-fused porphyrins 257.2ad (Scheme
257).1390 In these cyclizations, Pd(PPh3)4 and K3PO4 were
used, respectively, as the source of palladium and the base. The
UVvis spectra of compounds 257.2a and 257.2b exhibited
bathochromically shifted Soret bands (425 and 453 nm,
respectively) in comparison to the parent porphyrins
257.1ab. Under similar conditions, double cyclization on
the diphenyl derivative 257.3 was successfully conducted,
yielding two isomeric fused porphyrins 257.4 and 257.5. The
UVvis spectrum for the mixture of isomers showed the Soret
band at 424 nm. Under the above coupling conditions,
analogous bromoporphyrins did not produce annulated
products, indicating a requirement for the more reactive iodo
species.
Successful meso-aryl annulations of -brominated porphyrins
were subsequently reported by Chen and co-workers.1391
Porphyrins 258.2ad were obtained in moderate yields by
Chart 60. Products of Double Intramolecular Couplings of

2-Formylporphyrinsa
Structures C60.2 and C60.3 are proposed as alternatives.1292
treating compound 258.1 with 50 equiv of metallic zinc in

DMSO (Scheme 258). However, debromination of the parent
porphyrins, producing 258.2ad, was the dominant reaction in
all cases. The annulations could be completely inhibited in the
presence of 20 mol % of p-dinitrobenzene or hydroquinone,
indicating a radical nature of the process. In the following
report from the Chen group, the selectivity of the annulation
was considerably improved by using Pd catalysis.1392 A similar
approach was also used by Imahori et al. in their work on
cyclopenta[cd]porphyrin-based dye-sensitized solar cells.1393
Both the Zn-promoted1391 and the Pd-catalyzed1392 approaches
could be applied to the synthesis of doubly fused systems
258.5a and 258.6a, which formed from 258.4a with partial
debromination.
The quadruply fused target 258.7a was obtained in 2013 by
Ishizuka, Kojima, et al., when Pd nanoclusters derived from
[Pd(3-C3H5)Cl]2 were employed as the catalyst.1394 This new
procedure enabled the exploration of substituent eects in a
range of derivatives 258.7bf.1395 The lowest energy Q-band
was observed for 258.7a below 1000 nm, and the fused
porphyrin absorbed eciently across the entire visible range. In
the series 258.2a, 258.6, 258.8, and 258.7a, electrochemically
determined HOMOLUMO gaps became narrower with the
increasing number of fused rings. However, the lowering of the
LUMO level by ring-fusion was stronger than the correspondFL
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Scheme 257. Single- and Double-Intramolecular Pd(0)-Catalyzed Cyclization of Metalloporphyrins Bearing Iodo Substituentsa
Reagents and conditions:1390 (a) Pd(PPh3)4, K3PO4 (10.0 equiv).
Scheme 258. Cyclopenta[cd]fused Porphyrins via Heck-Type Cyclizationsa
Reagents and conditions: (a)1391 Zn (50.0 equiv), DMSO, 85 C; (b)1392 Pd2(dba)3CHCl3 (0.05 equiv), K2CO3 (10.0 equiv), DMF, 130 C;
(c)1394 [Pd(3-C3H5)Cl]2, PPh3, (n-Bu)4N(OAc), K2CO3, 1,4-dioxane.
Scheme 259. Synthesis of Indenoporphyrinsa
a
Reagents and conditions:1397 (a) Zn, propionic acid, CH3CH2CO2Na, >150 C; (b) NCS, CHCl3, overnight, rt; (c) (1) p-TSA, AcOH, 2 h, rt, (2)
H2, Pd/C, acetone, MeOH, Et3N; (d) TFA, CH(OMe)3, rt to 40 C; (e) p-TSA, DCM, MeOH, overnight, rt.
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Scheme 260. Surface-Assisted Cyclodehydrogenation of Tetraphenylporphyrinsa
Reagents and conditions:1399 (a) annealing, Ag(111) surface.
Scheme 261. Coverage- and Temperature-Dependent Metalation and Dehydrogenation of Tetraphenylporphyrin on Cu(111)a
Reagents and conditions:1400 (a) T, Cu(111). Green H atoms are removed in the following dehydrogenation step.
reduced, as judged by the chemical shifts of meso-protons (ca.

9.3 ppm).
Indeno-fusion was also achieved by means of surface
chemistry. Temperature-induced chemical modication of
tetraphenylporphyrin on Ag(111) produced structures with
entirely at conformations in which the meso substituents were
coplanar with the macrocycle.1398 The possibility of dehydrogenative coupling of substituents was conrmed by DFT
calculations. Room-temperature deposition of either 260.1a or
260.1b molecules onto a Ag(111) substrate led to the
formation of extended islands.1399 Annealing the free base
260.1a molecules to temperatures between 530 and 620 K for
10 min induced intramolecular dehydrogenation resulting in
planar derivatives 260.2a5a (Scheme 260). Upon annealing
the Ru complex 260.1b to 620 K, the same ring-closing
reactions took place; however, the occurrence of the four
reaction products is very dierent for both molecules. It was
found that the 2-fold symmetry of the 260.1a core, imposed by
the two central hydrogens, drives the selectivity of the reaction
at the periphery of the molecule toward 260.2a, as the major
product. Such selectivity could not be observed when triggering
the same annulation reaction in 260.1b or the corresponding
cobalt complex, wherein the macrocycle core has a 4-fold
symmetry. Annealing to temperatures above 670 K led to
polymerization reactions between molecules by CH activation
and formation of new intermolecular CC bonds similar to the
homocoupling of porphine on Ag(111) (Figure 5, section
7.3).1374
Using temperature-programmed desorption (TPD), three
main reactions of 5,10,15,20-tetraphenyl-21H,23H-porphyrin
260.1a with Cu(111), metalation, stepwise partial dehydrogenation to 261.3, and complete dehydrogenation of 261.3, were
identied using STM (Scheme 261).1400 At low coverage
ing rise of the HOMO level. The magnetic properties of these

cyclopenta-fused porphyrins indicated a contribution of
antiaromatic resonance forms resulting from the presence of
the additional double bond on the periphery. The zinc complex
258.9, which in contrast to the planar free base has a concave conjugated surface, was reported by Ishizuka, Kojima, et al. to
bind fullerenes C60 and C70.1396 Solid-state structures of these
complexes revealed a 2:1 stoichiometry, with two molecules of
258.9 enclosing one fullerene molecule, the latter being fully
covered by the concave porphyrin surfaces. In addition, a
crystal structure of the 1:1 complex with C60 was obtained, in
which the exposed part of the fullerene molecule formed a
interaction with C60 in the neighboring complex.
In 2011, Lash and co-workers developed an alternative
approach to indeno[1,2,3-cd]porphyrins, in which the indene
substructure was preassembled at the monopyrrole stage.1397 A
Knorr-type reaction of oxime 259.2 with 2-indanone 259.1 and
zinc dust in propionic acid gave indenopyrrole 259.3, which
was subsequently chlorinated to form 259.4 (Scheme 259).
Dipyrrolic intermediates were prepared in a reaction between
259.4 and -unsubstituted pyrroles 259.5ab in the presence
of p-toluenesulfonic acid, followed by hydrogenolysis of the
benzyl ester protective groups. The resulting compound 259.6
was converted into the corresponding dialdehyde 259.7 with
TFAtrimethyl orthoformate and then condensed with a
dipyrromethane dicarboxylic acid 259.8, providing indenoporphyrin 259.9 in 26% yield. The porphyrin gave a highly
modied UVvis absorption spectrum with three strong bands
showing up in the Soret region and a series of bathochromically
shifted Q bands that extended beyond 700 nm. The proton
NMR spectra of indenoporphyrins showed that the diamagnetic ring current for this porphyrin system was signicantly
FN
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(<0.36 molecules nm2), reaction rates were independent of

coverage. At higher coverage, metalation became faster, whereas
partial dehydrogenation was slower. In the metalation step,
release of one hydrogen molecule was observed. Intramolecular
dehydrogenation was observed to occur in two steps, each
associated with the abstraction of two hydrogen molecules,
yielding consecutively 261.2 and 261.3. Finally, liberation of 10
H2 molecules suggested the complete peripheral dehydrogenation of 261.3. The structure of the product was presumed to
involve either direct CC bonds between porphyrins or
organometallic copper linkages.
7.4.3. Other Cyclopenta-Fused Systems. In a contribution from Matsuo and co-workers, two types of thieno-bridged
porphyrins, 262.3 and 262.5, were synthesized by incorporating a thiophene ring across adjacent meso and positions.1401
In each case, the synthesis started from a SuzukiMiyaura
cross-coupling of meso-borylporphyrin 262.1 with 2-chloro-3bromothiophene and 3,4-dibromothiophene, respectively,
followed by intramolecular Heck reactions (Scheme 262).
confused pyrrole and the ortho-carbon of the adjacent meso-aryl

group (Scheme 263).1402 This reaction was not observed with
Scheme 263. Regioselective Ring Fusion in N-Confused
Porphyrina
Scheme 262. Synthesis of Thieno-Bridged Porphyrinsa
Reagents and conditions: (a) CF3COOH, air, toluene, reux, 5 h; (b)

AgBF4, CHCl3, rt.
other meso-substituents, which only yielded the corresponding

3,3-linked homodimers. The resulting indeno-fused product
263.2 remained aromatic, although a reduction of the diatropic
ring current was observed, consistent with the antiaromatic
resonance contributions characteristic of dehydropurpurin
systems. Mixing of a chloroform solution of 263.2 with
AgBF4 yielded a complex consisting of two indeno-NCP
subunits linked by the coordinated silver(I) ion.
7.4.4. Fused 7-Membered Rings. Even though
cyclohepta[cd]fused porphyrinoids have been obtained less
frequently than cyclopenta-fused systems, the diversity of
annulation strategies used for their synthesis is remarkable. A
classical approach, involving stepwise elaboration of the
substituent chain into the 7-membered ring and its subsequent
aromatization, was used by Gust, Moore, Moore, et al. for the
synthesis of the cyclohepta[cd]porphyrin C61.1 (Chart 61).1403
The 7-membered ring was found to be a reactive diene in
DielsAlder reactions. Quinone cycloadducts of C61.1 were
subsequently used for investigations of photoinduced electron
transfer.1404 Pandey et al. reported that a -vinyl substituent on
an imide-fused porphyrin (emeraldin) engaged into cycloaddition reactions with dimethyl acetylene dicarboxylate,
yielding, in addition to the expected -linked [2+4] cycloadduct, the meso-linked product C61.2.1405 Zinc tetraphenylporphyrin bearing a 2-chloro-1,1,2,2-tetrauoroethyl substituent at one position was observed by Chen, Guo, et al. to
produce the fused product C61.3 when subjected to a reductive
cycloaromatization reaction.1406 The reaction was proposed to
involve dithionite-induced formation of a radical intermediate,
which initially cyclized to form the 7-membered ring, to
undergo consecutive loss of two F anions. The diazepine C61.4
was obtained in 2014 by Senge et al. as a product of hydrazine
condensation of the corresponding dibenzoyl porphyrin
obtained by oxidative cleavage of a dehydropurpurin (cf.,
Scheme 211).1407
Reagents and conditions:1401 (a) Pd2dba3, PPh3, Cs2CO3, toluene/

DMF, 100 C; (b) Pd(OAc)2, PCy3HBF4, K2CO3, DMF, 155 C.
Compound 262.3 showed a clear antiaromatic contribution due

to its 20 conjugated circuit, whereas 262.5 exhibited a lesser
contribution of antiaromaticity because of the disruption of the
possible 24 circuit by the sulfur atom. The two-photon
absorption (TPA) cross section measured for compound 262.3
had a value of only 200 GM, about one-third of the value
determined for 262.5 at the same wavelength (550 GM). 262.5
showed Soret and Q bands typical of aromatic porphyrins. In
contrast, the corresponding bands of 262.3 were notably
attenuated, and weak NIR absorption was observable up to
1000 nm.
Chmielewski et al. reported that the acid-catalyzed exocyclic
ring formation in meso-tetrakis(3,5-dimethoxyphenyl)-2-aza21-carbaporphyrin 263.1 (N-confused porphyrin, NCP) took
place regioselectively between the external carbon of the
FO
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Chart 61. Porphyrins with [cd]Fused 7-Membered Ringsa
shifted (652 nm for cis-264.2c; 705 nm for trans-264.2b). In

the 264.3 family, the location of UVvisNIR absorption
bands was metal-dependent, with the copper species having
spectra further red-shifted than those of their palladium
analogues. For both the cis and the trans isomers, the most
intense absorption band occurs in the visible region ( = 540
579 nm). The Q-like bands of trans isomers exhibited a large
bathochromic shift relative to the spectra of their cis
counterparts ( = 850894 nm vs = 9941204 nm for the
cis and trans isomers, respectively). A similar rearrangement,
which occurred directly during the Lindsey synthesis, was
observed in 2012 by Hu and co-workers, leading to the singly
fused products 264.4.1409
7.5. Porphyrinoids with Polycyclic Subunits
7.5.1. Porphyrinoids with Benzannulated Bipyrrole

Units. The 1,8-dihydropyrrolo[3,2-g]indole substructure,
which may be viewed as a bay-annulated 2,2-bipyrrole, is a
common structural feature of several porphyrinoids.1188 These
systems typically derive from bipyrrole-containing macrocycles
(e.g., porphycenes, sapphyrins, or cyclopyrroles). The rst
example of such a molecule, dibenzo[cde,mno]porphycene
265.3a, was reported by the Vogel group in 1993 (Scheme
265).1410 The synthesis of 265.3a was achieved by reductive
carbonyl coupling of the dialdehyde 265.1 to give corresponding N,N-dihydroporphycene 265.2, an isolable compound, and
subsequent oxidation of the latter by means of DDQ. Waluk
and co-workers investigated the photophysics of 265.3ab by
stationary and time-resolved spectroscopy and quantum
chemical calculations.1411,1412 The absorption spectra of
dibenzoporphycenes were enriched, with respect to those of
porphycene, by the appearance of an electronic transition lying
between the Q and Soret bands. Both compounds were found
to be nonluminescent even at low temperatures. This lack of
the uorescence was in sharp contrast to nonfused porphycene
and its alkyl derivatives, which either showed strong emission
already at room temperature or recovered the radiative
Bonds formed in the annulation step are shown in red.
In 2004, Scott et al. presented a photoinduced oxidative

rearrangement of metalloporphodimethenes 264.1ad, which
produced intrinsically nonplanar metalloporphyrins cis- and
trans-264.2ad featuring two peripherally fused naphthocycloheptanone ring systems (Scheme 264).1408 Rigorous exclusion
of water and alcohols was necessary to avoid competitive
reactions. Further DDQ- and FeCl3-mediated oxidative
dehydrogenation generated almost perfectly planar ring
systems, cis- and trans-264.3b,d, bearing bis(naphthoazulenone) subunits. Among the 264.2ad derivatives, the trans
compounds reacted more slowly than their respective cis
isomers, requiring additional equivalents of oxidants and a
reductive aqueous workup. The Soret bands in the UVvis
spectra of naphthocycloheptanone derivatives appear at lower
energy than those of tetraphenylporphyrin and range from 466
nm (trans-264.2c) to 490 nm (cis-264.2b). The low-energy
electronic transitions for these porphyrins are also quite red-
Scheme 264. Oxidative Rearrangement of Dispiroporphodimethenes to Porphyrinsa
Reagents and conditions:1408 (a) h, DDQ (2 1.2 equiv), CH2Cl2, rt, 25120 min; (b) DDQ (7.2 equiv), FeCl36H2O (20 equiv), CH2Cl2, heat,
56 h; (c) DDQ (4.8 equiv), FeCl36H2O (10 equiv), CH2Cl2, heat, 15 min.
a
FP
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Scheme 265. Dibenzo- and Dinaphthoporphycenesa
properties as the temperature was lowered. Dierences in

relaxation rates relative to nonfused porphycenes were
rationalized in terms of the increased conformational exibility
of the fused system, which was presumed to be nonplanar.
Using suitable naphthobipyrrole precursors and Vogels
strategy, Sessler and co-workers synthesized dinaphthoporphycenes 265.4ab.1413 These two systems showed consistent
electronic spectra, with Q bands at 725, 671, and 556 nm, and a
Soret band at 404 nm. 265.4b was weakly uorescent in
solution and displayed two reversible oxidation processes at
0.89 and 1.24 V vs SCE. Similar dinaphthoporphycenes were
obtained in a one-step couplingdehydrogenation synthesis by
Panda et al.,1414 who also reported the synthesis of a
nickel(II)1414 and copper(II)1415 complexes, 265.4cd. Nonlinear absorption measurements performed for free-base
dinaphthoporphycenes and their complexes revealed the
presence of two-photon absorption (TPA) at low peak
intensities and three-photon absorption at higher peak
intensities.1416 Ultrafast excited-state dynamics of dinaphthoporphycenes were investigated using femtosecond and picosecond degenerate pumpprobe techniques at 600 and 800
nm, respectively.1417 Femtosecond pumpprobe data indicated
photoinduced absorption at 600 nm resulting from twophoton/single-photon excitation, whereas picosecond pump
probe data demonstrated photobleaching, which was a
consequence of three-photon absorption. Fast (100120 fs),
medium (13 ps), and slow (710 ps) lifetimes were observed
and attributed, respectively, to the intramolecular vibrational
relaxation, internal conversion, and nonradiative decay to the
ground state.
Reagents and conditions:1410 (a) Ti(0); (b) DDQ.
Scheme 266. Synthesis of Benzo- and Naphthodipyrrole Macrocyclesa
Reagents and conditions: (a)1420 DMF/POCl3; (b)1420 LiAlH4; (c)1420 (1) TsOH, (2) Et2O/O2; (d)1420 TsOH; (e)1423 (1) TFA, (2) DDQ, TEA;
(f)1424 (1) TFA, DCM, 48 h, (2) DDQ, 1.5 h, (3) TEA; (g)1424 Na2S2O4; (h)1424 TEA or MnO2; (i)1424 TfOH or HClO4; (j)1424 Cl or Br or I;
(k)1424 Me10Fc or HI; (l)1424 HX (X = Cl, Br, I, CF3COO, MeSO3).
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The inner coordination chemistry of dinaphthoporphycenes

is limited,1414,1415 presumably because of the unfavorable
rectangular geometry of the coordination core. The outer
benzene rings of dinaphthoporphycene can however act as 6
ligands, and metallocene complexes with Rh and Ir, 265.5ac,
were prepared by the Sessler group.1418 Using electrochemistry
data, this type of coordination was shown to enhance electronacceptor properties of the macrocycle. An attempt to synthesize
a PdII-complex of 265.4b with Pd(OAc)2 in reuxing acetic acid
led to the isolation of a dipalladium complex 265.6, where the
porphycene ligand is deformed into a bowl-like shape.1419
When reuxed with Pd(acac)2 in o-dichlorobenzene and
pyridine, the same ligand produced the mono-PdII complex
265.7, in which the Pd center is bound to two adjacent core
nitrogens and one acac ligand, thereby leaving the remaining
two nitrogens uncoordinated. The UVvisNIR absorption
spectra of the two metalloporphycene complexes 265.6 and
265.7 reected the signicant deformation of the macrocycle.
For example, compound 265.6 showed a broad split Soret band
at 383 and 420 nm, with drastically reduced absorption
intensity as compared to the corresponding NiII- and CuIIcomplexes.1414,1415 Unlike other dinaphthoporphycenes and
their metal complexes, each of which possessed four Q-type
bands, 265.6 showed only two Q absorptions, red-shifted
relative to the planar complexes. Complex 265.7 also exhibited
two Q bands, which were blue-shifted relative to those of
265.6. Electrochemical analyses of both metal complexes
showed the presence of two reversible one-electron reduction
and two one-electron oxidation events.
In 2005, benzo[cde]sapphyrin 266.6 was synthesized by Lee
and co-workers through the typical acid-catalyzed [3+2]
condensation of diformylbenzodipyrrole 266.4 and tripyrrane
dicarboxylic acid 266.5, followed by air oxidation (Scheme
266).1420 Intermediate 266.4, obtained from the unsubstituted
266.1 by a double formylation sequence, proved to be less
reactive than simple bipyrroles, and this lack of reactivity was
thought to account, in part, for the low isolated yield of 266.6.
The absorption spectra of free-base 266.6 showed a Soret-like
band at 466 nm, which was only slightly red-shifted in the
ditosylate salt 266.62TsOH (469 nm). The strongestabsorbing Q-band in 266.6 appeared at 727 nm, whereas in
the ditosylate, the major Q-band at 703 nm was accompanied
by a weaker feature at 748 nm. Using a related approach,
Sessler and co-workers obtained the dioxa analogue C62.1
(Chart 62). 1421 The dication of this compound was
demonstrated to weakly bind Cl and F anions, whereas binding
of phenols was observed for the free base. Naphthosapphyrins
C62.2ab, similarly synthesized by Panda et al., were
investigated for their conformational dynamics and excitedstate properties.1422 In neither of these systems was pyrrole
inversion observed, regardless of the amount of acid added.
Because of the higher optical nonlinearity of the free bases
C62.2ab, in comparison with their salts, two-photon
absorption was observed even at lower peak intensities.
Excited-state dynamics of C62.2ab were studied by
degenerate and nondegenerate pumpprobe techniques,
revealing decay times of high-lying excited states in the picoand nanosecond regimes.
In 2011, fully aromatic dinaphthorubyrin 266.8 and pyrroleinverted naphthosapphyrin 266.9 were synthesized via a lowyielding mixed pyrrolealdehyde condensation, followed by
DDQ oxidation (Scheme 266).1423 The absorption spectrum of
the free base 266.8 was characterized by a split Soret band (max
Chart 62. [bcd]-Fused Expanded Porphyrins
= 528 and 562 nm), and by two Q-bands appearing at 841 and
875 nm. The monoprotonated form displayed a similar UVvis
spectrum, albeit with slightly bathochromically shifted bands at
532, 590, and 877 nm, respectively. In the dication, a relatively
strong Soret-like band appeared at 557 nm, accompanied by
multiple Q-bands at 733, 823, and 922 nm. The neutral and
protonated forms of 266.8 all gave rise to appreciable
uorescence emission, showing a red shift upon protonation
of the macrocycle. In naphthosapphyrin 266.9, one pyrrole
adopted an inverted geometry; however, the reinversion was
observed upon monoprotonation, apparently caused by intramolecular hydrogen-bonding stabilization. In the presence of
excess acid, 266.9 was observed to yield a diprotonated form
with spectral features again consistent with pyrrole inversion.
The most red-shifted bands at UVvis absorption spectra of
free-base and dicationic form of naphthosapphyrin 266.9
occurred at 781 and 784 nm, respectively. In contrast, the
monoprotonated 266.9 exhibited a featureless, broad Q-like
band. Core-modied macrocycles C62.3ab, that is, dithia- and
dioxa- analogues of dinaphthorubyrin 266.8, were synthesized
by Lee and co-workers.1425 Oxasapphyrin C62.4, reported in
the same work, shared the inverted conformation with 266.9,
whereas the corresponding thia derivative had a noninverted
structure analogous to that of C62.1.
Trinaphthorosarin 266.10, described in 2012 by Sessler and
co-workers, is a near-planar macrocycle with strong antiaromatic characteristics, consistent with its 24 -electron
conjugation (Scheme 266).1424 In this regard, it diers from
the nonfused parent rosarin system, which is nonplanar and
consequently nonaromatic. 266.10 was synthesized in a direct
condensation between 1,10-dihydrobenzo[e]pyrrolo[3,2-g]indole 266.7 and pentauorobenzaldehyde, under typical
conditions. 266.10 could be reversibly reduced to the aromatic,
26 -electron monocation [266.10-H]+, which was characterized in the solid state as the chloride salt. However, when
266.7 was treated with HCl or HBr, a paramagnetic species was
produced, which was identied as the one-electron reduction
product, radical dication [266.10-H3]2+. When HI was used,
the reduction proceeded further, yielding ultimately the
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aromatic monocation [266.10-H]+, and I3 as the oxidized

byproduct. The inuence of the anion was further demonstrated in a two-step experiment, in which protonation with
acids such as TfOH or HClO4 produced the tricationic species
[266.10-H3]3+, which underwent reduction upon addition of
the appropriate halide ion. The acid/anion-induced reduction
of 266.10 was gradually reversed upon addition of base.
Cyclo[4]naphthobipyrroles 267.2ad,1426,1427 peripherally
fused derivatives of cyclo[8]pyrrole,1213 were independently
synthesized by the groups of Sessler1426 and Panda1427
(Scheme 267). In both reports, target compounds 267.2
chromophores, characterized by the energy dierence between

the LUMO orbitals being much larger than the energy
dierence within the HOMO pair. On the basis of the
HOMO LUMO inequality, relative intensities in
absorption and magnetic circular dichroism (MCD) can be
predicted, as well as the pattern of MCD signs.
7.5.2. Cyclooctatetraene-Fused Systems. The synthesis
of doubly linked corrole dimer 268.4, reported by the Osuka
group, began with a palladium-catalyzed oxidative coupling of
268.1 using chloroacetone as an oxidant, which aorded the
2,2-linked corrole dimer 268.2 (Scheme 268).1430 The latter
species was further cyclodehydrogenated by means of DDQ,
providing 268.3 as the only product. Reduction of 268.3 with
NaBH4 gave 268.4 quantitatively and proved to be reversible by
using DDQ. Both doubly linked corrole dimers 268.3 and
268.4 were subjected to metalation with appropriately charged
ions, yielding respectively bis-cobalt(III) and bis-zinc(II)
complexes. The oxidized form 268.3 and its zinc(II) complex
were the rst reported porphyrinoids to exhibit a biradicaloid
character. Upon treatment of 268.3 with pyridine and its parasubstituted derivatives in CH2Cl2 or under neat conditions,
regioselective nucleophilic pyridination took place at the most
sterically congested positions (the bay region), providing
stable zwitterionic products that showed a negative solvatochromic eect.1431
7.5.3. Thiophene-Fused Systems. A range of porphyrinoids containing polycyclic thiophene-based subunits were
synthesized via extensions of the Lindsey porphyrin synthesis.
Dithieno[3,2-b:2,3-d]thiophene was found to be a particularly
versatile building block, which can be viewed as a functional
analogue of the 2,2-bipyrrole unit that contains two sulfur
atoms instead of nitrogens and is rigidied by fusion of the
central thiophene ring. Using this analogy, the macrocycles
C63.1ab and C63.2ac, synthesized by Chandrashekar and
co-workers,1432 can be described as modied rubyrins (Chart
63). Further extension of this approach provided access to
planar heptaphyrins C63.31432 and C63.6ab,1433 sapphyrins
C63.5ab,1434 and the gure-eight octaphyrins C63.4ab,1435
In comparison with their nonfused analogues, these systems
often displayed rigidied conformations and enhanced
aromaticity. In the case of C63.4a, protonation using TFA
resulted in the formation of a near-planar dication containing
two inverted pyrrole rings, which had a strongly paratropic
character, consistent with its 36-electron conjugation, and was
characterized in the solid state. Aromatic, [22]annulenoid
porphyrin analogues C63.79 containing thieno[3,2-b]thiophene moieties were reported in 2014 by Rath and coworkers.1436 The optical bandgap in those systems was
Scheme 267. Synthesis of Cyclo[4]naphthobipyrrolesa
Reagents and conditions: (a)1426,1427 FeCl3, H2SO4.
were prepared via the FeCl3-mediated oxidative coupling of dialkylnaphthobipyrroles 267.1ad. The conditions were
modulated to optimize the formation of the desired products,
that is, by extension of the reaction time, increasing the amount
of the oxidizing agent, and using Ce(SO4)2 monohydrate
instead of FeCl3.1427 Marginal red shift of the B-bands as
compared to nonfused cyclo[8]pyrroles was observed in the
absorption spectra of 267.2; however, naphtho-fusion had a
considerable impact on the NIR-located L bands, which
showed large red shifts (up to 228 nm) and increased
intensities relative to the B bands. The singlet excited state of
267.2a was short-lived, with a single exponential decay with a
half-life of 0.5 ps, and the two-photon absorption value for this
compound was 3400 GM.1426
Dispersion studies of nonlinear optical (NLO) properties of
the cyclo[4]naphthobipyrroles 267.2ac were reported by
Venugopal Rao et al.1428 Two-photon absorption was the
dominant mechanism observed in these molecules, with high
NLO coecients (and corresponding two-photon cross
sections) observed in the 600800 nm spectral range. Further
studies on cyclo[4]naphthobipyrroles 267.2ac properties
encompassing their structure, electronic states, and anionbinding were carried out by Waluk et al.1429 Alkyl-substituted
cyclo[4]pyrroles 267.2ac are examples of negative-hard
Scheme 268. Synthesis of Doubly Linked Corrole Dimersa
Reagents and conditions:1430 (a) PdCl2(dppb), chloroacetone, THF, H2O, 70 C, 6 h; (b) DDQ, toluene, 50 C, 1.5 h; (c) NaBH4, THF, MeOH,
rt, 30 min; (d) DDQ.
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Chart 63. Porphyrinoids Containing Polycyclic Thiophene-Based Subunitsa
Bonds formed in the macrocyclization step are indicated in red.
relatively insensitive to peripheral fusion, with the onset of NIR

absorption observed in each case at ca. 10001100 nm.
Tetraphyrin C63.10 containing a thieno[3,2-b]pyrrole
subunit was developed in 2012 by Shen et al.1437 In the solid
state, the compound was observed to exist as the peripherally
protonated tautomer (shown in Chart 63) characterized by a
cross-conjugated valence structure. 1H NMR data apparently
suggested the presence of several tautomers and possible
involvement of paratropic, [20]annulenoid tautomers with
double inner protonation. Computational studies on six
tautomers of C63.10 and its unsubstituted form indicated
that the aromatic properties of the macrocycle were strongly
inuenced by the ethoxycarbonyl substituent at the pyrrole ring
of the thienopyrrole moiety.1438 The antiaromatic character of
C63.10 could also be deduced from the solution absorption
spectrum, which displayed a broad band in the 7001000 nm
range, corresponding to a dipole-forbidden S-type transition.
C63.10 could be reduced chemically and electrochemically to
an ESR-active radical species. A porphyrinoid-like macrocycle
containing four naphtho[2,1-b:3,4-b]dithiophene subunits,
C63.11, was synthesized by the Hoger group via an oxidative
FeCl3-mediated cyclooligomerization.1439 A bis-PDI-substituted
derivative of C63.11 was shown to self-organize on the TCB/
HOPG interface via Stron attractive forces between the outer
PDI units.
7.5.4. Systems with Acene and Heteroacene Subunits.
In 2002, Sessler and Furuta et al. described a series of expanded
porphyrinoids 269.2ac, combining pyrrole, quinoxaline, and
anthracene subunits.1440 The macrocycles were obtained by
Schi-base condensation of the dialdehydes 269.1ac with 1,8diaminoanthracene (Scheme 269) and were shown to adopt a
nonplanar conformation with two cavities in the solid state.
Because of macrocyclic preorganization, these systems displayed augmented anion binding anities toward uoride and
dihydrogen phosphate anions in organic solution, relative to the
noncyclic 269.1a. Positive allosteric binding of uorides was
Scheme 269. Synthesis of AnthraceneAuinoxaline

Expanded Porphyrinsa
a
Reagents and conditions:1440 (a) 1,8-diaminoanthracene, HCl,
toluene/MeOH.
demonstrated, indicative of the cooperative behavior of the two

receptor sites.
Phenanthrene and its heterologues are attractive subunits for
constructing macrocycles, especially when anchored at
positions 3 and 6. The majority of such systems designed to
date, usually based on 1,10-phenanthroline, have been typically
classied as cyclophanes and are discussed in section 7.7. A
hybrid phenanthrolinedipyrrin porphyrinoid 270.3 was
reported in 2010 by Naruta et al. (Scheme 270).1441 The
macrocycle was obtained by acid-catalyzed condensation of the
bis(methylenemalonate) 270.1 with phenyldipyrromethane
270.2, followed by DDQ-mediated oxidation. The macrocycle
was found to be nonplanar, with a relatively small monoanionic
coordination cavity, and displayed selective Mg2+ complexation
in the presence of Na+, K+, and Ca2+, accompanied by a red
shift and intensity enhancement of uorescence. Analysis of
various MgX-270.3 systems (X = anion) revealed signicant
substitution eects on their chemical, electrochemical, and
photophysical properties, as well as on the Mg2+-cation
anities.1442 The uorescence properties of MCl-270.3
reected the eect of donor-excited photoinduced electron
transfer (d-PET) processes from the dipyrrin subunit (as a
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Scheme 270. Porphyrinoids with Phenanthroline Moietiesa
Reagents and conditions: (a)1441 (1) triuoroacetic acid, CH3CN, rt, 3 days, (2) DDQ and triethylamine, 1 h.
dipyrrin chromophores, but the uorescence was characterized

by a low quantum yield (<0.05) and a signicant Stokes shift.
The related tetrathia derivatives C64.2ac were also
synthesized, apparently attaining complete macrocyclic conjugation with a 30-electron circuit. These compounds were
deeply colored with a major absorption maximum at ca. 800
nm, but they gave no observable 1H NMR spectra, nor were
they characterized in the solid state. The macrocyclic structure
of C64.2ac was conrmed indirectly by reducing these
species to their meso-saturated derivatives with NaBH4.
Phenanthriporphyrin 271.3, reported in 2015 by LatosGrazynski and co-workers, was obtained in two steps from the
phenanthrene dicarbinol 271.1, via the usual Lindsey-type
chemistry (Scheme 271).1446 The antiaromatic character of
donor site) to the 1,10-phenanthroline acceptor subunit. In

subsequent work, 270.3 was shown to form copper and nickel
hexauorophosphate complexes.1443 The Ni-270.3 complex
exhibited solvato- and termochromism, caused by switching
between low-spin square planar and high-spin octahedral
geometry.
In subsequent work, Naruta and co-workers synthesized a
related expanded macrocycle 270.4 using a similar strategy.1444
Protonation of 270.4 resulted in the formation of a stable
tricationic species 270.5, which was identied as an oxidized
form of 270.4. 270.5 had a distinct biradicaloid character, and a
singlettriplet gap of 470 cm1 was determined on the basis
of temperature-dependent magnetic susceptibility data. The
formation of 270.5 in the presence of acid was associated with
the appearance of extended NIR absorptions, and the process
could be reversed by addition of base. Direct treatment of
270.4 with oxidants such as DDQ or cerium ammonium nitrate
without the addition of acid did not generate the biradicaloid.
The role of dioxygen in the acid-induced formation of 270.5
was excluded by control experiments, but the actual oxidant was
not identied.
The triphenylenedipyrrin hybrid C64.1, synthesized by
Cammidge and co-workers via a Lindsey-type condensation of
the appropriately substituted 2,11-di(pyrrol-2-yl)triphenylene,
was observed to adopt the C2h-symmetric conformation in
solution and in the solid state1445 (Chart 64; for related
triphenylene cyclophanes, see C69.911, section 7.7). The
absorption and emission spectra of C64.1 were typical of
Scheme 271. Phenanthriporphyrina
Chart 64. Expanded Porphyrin-Like Structures Based on

Twinned Triphenylenes1445
Reagents and conditions:1446 (a) (1) pyrrole, BF3Et2O, reux 17 h,
(2) triethylamine; (b) (1) benzaldehyde, BF3Et2O, CH2Cl2, 2 h, (2)
DDQ; (c) (1) PCl3, TEA, reux, 2 h, (2) CH2Cl2/MeOH, air.
a
271.3 was apparent from its 1H NMR and UVvis spectra and
was rationalized in terms of [16]- and [20]annulenoid
conjugation pathways. A phosphorus(V) complex 271.4,
which can be viewed as a -expanded, hypervalent phosphole
derivative, was obtained by reacting 271.3 with PCl3 and
characterized using NMR spectroscopy.
7.5.5. Systems with Macrocyclic Subunits. Incorporation of macrocyclic subunits into even larger cyclic structures
has been an important concept for the design of ultralarge
cavities and loops. These systems, usually assembled using
acetylene1447 or biaryl coupling chemistry, often deviated
considerably from planarity and showed signicant kinking,
resulting in interrupted -conjugation of the supermacrocycle
(for recent examples, see, e.g., nonplanar cycloporphyrins from
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Chart 65. Porphyrin-Based Supermacrocycles
the Osuka group14481450). Osuka and co-workers developed

several classes of cyclic porphyrin assemblies, which displayed
near-planar or smoothly distorted systems, at least for certain
supermacrocycle sizes (Chart 65). Thiophene bridged systems
C65.1ab and their Zn and Ni complexes, as well as the linear
oligomer C65.3a, were synthesized in 2008 by means of Suzuki
coupling cyclooligomerizations.1451 The Ni complex of C65.3a
was also prepared via PaalKnorr cyclization of the
corresponding diethynyl-linked cyclotrimer.1452 The Ni complexes of C65.1ab showed relatively planar conformations in
the solid state, with noticeable ruing of the thiophene
rings.1451 The electronic spectra were signicantly perturbed,
relative to the monomers with broadened Soret bands and Q
absorptions extending beyond 600 nm. The Zn complexes were
weakly uorescent, showing maximum emission in the 650
700 nm range. TPA cross sections for these systems were large,
reaching 17 300 GM for C65.3a. meso-Bridged cyclooligomers
containing bithiophene linkers were also obtained with n = 35
(C65.4ac and their Zn complexes).1453 In these systems, the
electronic communication between porphyrin subunits was
apparently weaker, although upon protonation with TFA,
compound C65.4a yielded an absorption spectrum with an
unusually strong red-shifted Q-band at 788 nm, indicating an
improved supermacrocyclic conjugation. Further examples of
related systems were provided in 2015 by Song et al.1454 who
prepared the azobenzene-linked macrocycles C65.3bd.
Linear, pyridine-bridged oligomers C65.1cd were obtained
using a similar strategy.1455 Because of the dierent geometry of
the pyridine linker, these oligomers were signicantly, although
smoothly curved, and this curvature was further increased in the
palladated derivatives C65.2ab. Very large TPA cross sections
were recorded for these oligomers, up to 24 000 GM for
C65.2b. The inherent curvature of these oligomers was
subsequently employed in the synthesis of a tetraporphyrin
nanobarrel capable of binding a C60 molecule.1456 Pyridinelinked cyclooligomers with n up to 8 (C65.3eh) were also
reported, with considerably nonplanar structures.1457
Supermacrocyclic structures can also be constructed by
introducing a conjugated strap into an expanded porphyrin
ring. Examples of this approach were provided by Osuka and
co-workers, who synthesized strapped [26]hexaphyrins C66.1
3 via condensation of a tripyrrane with 1,3-diformylbenzene,
2,5-diformylthiophene, and 2,5-diformylpyrrole, respectively
(Chart 66).1458 These internal straps were found to modulate
Chart 66. Internally Aromatic Strapped Hexaphyrins1458
the eective conjugation networks of C66.13. The eect was

negligible for the 1,3-phenylene strap present in C66.1, whereas
the 2,5-thienylene strap contributed to the macrocyclic
conjugation, producing roughly equal contributions of [26]hexaphyrin and [18]thiaporphyrin circuits in C66.2. In the case
of C66.3, the presence of the 2,5-pyrrylene linker resulted in a
predominant [18]porphyrin contribution. Related strapped
systems include a vinylene-bridged hexaphyrin by Suzuki and
Osuka1459 and a trithia analogue of C66.2 reported by
Chandrashekar, Kim, and co-workers,1460 and p-phenylenebridged decaphyrins from the Osuka group.1461
7.6. Internally Fused Porphyrinoids
Introduction of conjugated internal bridges inside porphyrinlike macrocycles produces subunits consisting of at least three
fused rings that are macro-fused to the major macrocyclic ring.
The most typical ways of achieving internal bridging are (1)
addition of bridging units, usually one- or two-atoms long,
producing, respectively, 6- and 7-membered rings, (2) N-fusion
of adjacent pyrrole subunits, and (3) meso-substituent fusion to
an adjacent pyrrolic nitrogen. The latter two reaction types
result in the formation of a ve-membered ring. In expanded
porphyrinoids, the distinction between peripheral and internal
modications is often blurred, because of the nonplanar
conformations of such large macrocycles. However, for
simplicity, all modications involving at least one inner
position in the macrocycle, usually a pyrrolic nitrogen, will be
considered internal fusion. The following section focuses on the
structural diversity of existing internally fused porphyrinoids
and key reactivity aspects. The reactivity and coordination
chemistry of internally modied porphyrin analogues has been
reviewed recently by several authors.1182,1190,14621464
7.6.1. Regular Porphyrins. Porphyrin derivatives containing fully conjugated internal bridges are usually synthesized via
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rearrangements of organometallic metalloporphyrin complexes.

The vinylidene-bridged species 272.1, reported in 1981 by
Gold and co-workers, was obtained by FeCl3-mediated
oxidation of the corresponding porphyrinatoiron(II) diarylvinylidene complex (Scheme 272).1465 Setsune, Dolphin, et al.
developed a synthesis of vinylene-bridged porphyrins of the

general structure 272.2, which were generated via rearrangement of CoIII porphyrins.14661468 Their approach was
extended in 2011 by Vaid, who successfully prepared a tetrap-tolylporphyrin with a CC unit at its center.1469 In the rst
step, cobalt porphyrin 272.3 was reacted with diiodoacetylene
under oxidative conditions, yielding the diiodovinylene
intermediate 272.4. Reduction of 272.4 with 2 equiv of SmI2
in THF gave the internally bridged isophlorin 272.5, with a
distinct paratropic character. The skeletal framework in 272.5
consists exclusively of peri-fused 5-, 6-, and 7-membered rings
and can be named 2a1,3a1,6a1,9a1-tetraazaheptaleno[2,1,10,9cdef:4,5,6,7-cdef ]di-s-indacene. The small size of the CC
fragment resulted in a pronounced ruing of the porphyrin
ring in 272.5. Oxidation of 272.5 with 2 equiv of AgOTf in
THF yielded the diatropic dication 272.52+ in the form of a
triate salt. The presence of the internal double bond in
272.52+ was seen to cause a splitting of the normally degenerate
LUMO level and a large decrease in the HOMOLUMO gap,
while the positive charge and tolyl groups led to additional
charge-transfer-like transitions in the visible absorption
spectrum.1470 The small HOMOLUMO gap and rued
structure were responsible for a very short excited-state lifetime
of 10 0.3 ps. A 2D polymer consisting of fused, unsubstituted
272.5 units was recently considered theoretically, with
proposed use in fuel cell applications.1471 Vaids work bears
relationship to the 2007 report by Brothers, Siebiert, et al.,
which described the preparation of the extremely air- and
moisture-sensitive diboranyl species 272.6 and 272.62+.1472 In
analogy to the CC porphyrin, the two oxidation levels of
272.6 were described respectively as isophlorin- and porphyrinlike, on the basis of their 1H NMR spectra.
7.6.2. N-Confused Porphyrins. In 1999, Furuta, Osuka, et
al. obtained N-fused porphyrin 273.2, a new type of
porphyrinoid with a built-in pyrrolo[3,2-b]pyrrolizine fragment
(Scheme 273).1473 Spontaneous formation of 273.2 was rst
observed when a pyridine solution of the brominated Nconfused porphyrin (NCP) 273.1a was left at room temperature for 8 h. NFP is green in solution (in contrast to NCP,
which has a red color) and is almost nonuorescent. The
absorption spectra recorded in CH2Cl2 showed the lowestenergy Q-band of 273.2 at 957 nm, which was bathochromically shifted by about 200 nm in comparison with 273.1a.
Scheme 272. Internally Fused Porphyrinsa
Reagents and conditions:1469 (a) (1) diiodoacetylene, FeCl3, CH2Cl2,

22 C, 1 h, (2) K2CO3(aq), CH2Cl2; (b) SmI2, THF, 22 C, 1.5 h; (c)
AgOTf, THF, 22 C, 15 min.
Scheme 273. N-Fused Porphyrin and Its Derivativesa
Reagents and conditions: (a)1473 pyridine, 8 h; (b)1473 NaOMe in MeOH, CH2Cl2, 30 min; (c)1474 Re2(CO)10, 1,2-dichlorobenzene, 160 C, 36 h.
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Scheme 274. Syntheses and Complexation of Etheno-Bridged NCPa
Reagents and conditions:1488 (a) Bu4NF; (b) NaOMe, THF, 23 C, 4 h; (c) NaOMe, THF, 23 C, 30 min; (d) Bu4NF, CH2Cl2, 23 C, 72 h; (e)
[RhCl(CO)2]2, AcONa; (f) SiO2; (g)1487 NaOMe, THF, 23 C, 4 h.
When subjected to the base-induced ring-opening conditions, ethynyl-substituted NFP 274.1b1477 unexpectedly
yielded the etheno-bridged N-confused tetraphenylporphyrin
274.4 with perfect regioselectivity.1487 Similarly, the expected
ring-opening product 274.3a was not observed for the
desilylated 274.2, which also produced 274.4.1488 The ringopened product 274.3b was however obtained from the TIPSsubstituted 274.1b, and was subsequently deprotected to yield
274.4. The unique dipyrrolo[1,2-a:3,4-d]azepine substructure
present in 274.4 considerably aects the electronic structure of
the NCP ring system, leading to a strong deformation of the
Soret band and a red shift of the lowest-energy Q-band.1487 A
dinuclear Rh complex 274.5, obtained by metalation of 274.4,
was found to partially decompose on silica gel, yielding the
lactam derivative 274.6.
Water-soluble NFP derivatives were obtained by conjugation
with peptides1489 and introduction of pyridinium substituents,1490 whereas the thiol-induced ring-opening reaction was
explored as a means of bioconjugation.1491 Tuning of optical
properties of NFP was achieved by 21-substitution with
electron-withdrawing groups, such as CN or NO2, which was
found to induce relatively weak NIR uorescence (F = ca. 5.0
104) with large Stokes shifts and unusually short lifetimes
(ca. 13.5 ps), consistent with the occurrence of an ESIPT
process.1492
Doubly N-fused porphyrin (N2FP, 275.4) was synthesized in
2008 by Furuta and co-workers.1493 Initially, N-confused Nfused porphyrin 275.2 was directly prepared by acid-catalyzed
[2+2] condensation of the N-confused dipyrromethane
derivative 275.1 (Scheme 275). Next, 275.2 was brominated
with 1,3-dibromo-2,2-dimethylhydantoin, and the resulting
tribrominated product 275.3 was treated with Hunigs base
to aord 275.4. Doubly N-fused porphyrin 275.4 exhibits
exceptionally long-wavelength absorption for an 18 aromatic
system (in excess of 1600 nm in toluene) and had the
narrowest HOMOLUMO energy gap (1.24 eV, calculated on
the basis of electrochemical measurements) of all reported
neutral [18]annulenoid compounds. N2FP is nonuorescent
and yields a TPA cross-section value larger than NFP (3600
GM vs 2000 GM), consistent with the more ecient
conjugation.1494
22-Methylated NCP derivative 276.1 subjected to reaction
with Re2(CO)10 produced, in addition to the 273.5 species
described above, also the N-heterocyclic carbene complex
276.2 (Scheme 276).1495 In this molecule, the formation of the
carbene bridge creates a tricyclic pyrrolo[3,4-f ]indolizine
substructure. Interestingly, no carbene complex was formed
The fusion process leading to NFP is heavily dependent on

the peripheral and inner substitution of the NCP macrocycle1475 and is thought to proceed via the pyrrole-inverted
conformer of NCP (e.g., 273.1a). The resulting NFP structure
is eectively planar, demonstrating the remarkable exibility of
the NCP ring. 273.2 was unstable in basic media; for example,
it was converted to the nonfused 273.1b when treated with
NaOMe/MeOH. A similar ring-opening reaction of NFP was
induced with thiophenols, which similarly added to position
3.1476 The latter ring opening could be reversed by radicalmediated desulfurization using tributyltin hydride and AIBN.
21-Bromo-substituted NFPs are reactive in palladium-catalyzed
cross-coupling reactions under Suzuki or Stille conditions,
aording the corresponding 21-aryl or arylethynyl derivatives
(cf., 274.1, Scheme 274).1477 In the case of the 21unsubstituted NFP, oxidative formation of the 2121-linked
dimer 273.3 was induced using AgOTf.1333
The contracted inner cavity of 273.2 and related derivatives
acts as a tridentate, monoanionic ligand and can bind certain
metals and nonmetals. In particular, the Re complex 273.5
could be obtained not only from the corresponding NFP ligand
but also by directly reacting the 3,21-unsubstituted NCP 273.4
with Re2(CO)10.1474 The complex was suciently inert to
undergo substitution reactions at position 21 without
demetalation,1478 and was also oxidized to yield the
trioxorhenium(VII) complex 273.6, characterized by a
particularly red-shifted electronic spectrum.1479 The latter
species showed a catalytic activity in deoxygenation of pyridine
N-oxides.1480 Upon deprotonation, the NFP core is isoelectronic with the cyclopentadienyl anion. To demonstrate this
analogy, the Furuta group prepared a range of metal complexes
via direct metalation of NFP, including a ferrocene-like doubledecker iron(II) system,1481 as well as Mn(CO)31482 and
Ru(CO)2Cl1483 species.
Latos-Grazynski and co-workers explored coordinationinduced internal fusions in reactions of NCP with PhBCl2
and PCl3, which yielded complexes with boron(III) (273.71484)
and phosphorus(V) (273.81485), respectively. In 273.8, the
NFP macrocycle was reduced to the isophlorin-like oxidation
level. A similar N-fused isophlorin complex obtained for 21telluraporphyrin was successfully oxidized to the corresponding
dication 273.9, exhibiting aromatic porphyrin-like conjugation.1486 The above nonmetal insertion chemistry generates, in
addition to the fully conjugated species presented here, also a
variety of products characterized by interrupted conjugation
in the macrocycle.
FX
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Scheme 275. Preparation of Doubly N-Fused Porphyrin1493a
Scheme 277. Synthesis of Imino-Fused N-Confused

Porphyrinsa
Reagents and conditions:1496 (a) R-CHO, p-TsOH, toluene, reux.
carbonyl bridge linking the internal carbon with one of the

internal nitrogens (Scheme 278).1497 The reaction took place
Reagents and conditions: (a) (1) BF3Et2O, CH2Cl2, 23 C, 1 h, (2)

DDQ, CH2Cl2, 23 C, 1 h; (b) 1,3-dibromo-2,2-dimethylhydantoin,
CH2Cl2, 23 C, 1 h; (c) i-Pr2EtN, CH2Cl2, 23 C, 6 h.
Scheme 278. Carbonyl-Bridged N-Confused Porphyrinsa
in the analogous reaction of the isomeric 24-Me NCP ligand,

whereas the C-methylated isomer 276.3 yielded a mixture of
276.2, the isomeric NHC complex 276.4, and 273.5. Despite
its distinct carbenic character, 276.2 exhibited considerable
stability and could be puried by column chromatography
under ambient conditions.
Scheme 276. Reactions of Inner-Methylated N-Confused
Porphyrins with Re2(CO)10a
a
Reagents and conditions:1497,1498 (a) (CH2O)n, Et3N, toluene, reux;
(b) triuoroacetic acid, toluene, reux, 20 min.
with an ca. 90% regioselectivity, providing additionally smaller

amounts of the isomeric products 278.3ad. In the presence of
acid, substituent fusion was induced for the alkoxyarylsubstituted derivatives 278.2cd, yielding products 278.4c
and 278.4d, each containing a system of ve ortho-fused rings.
The carbonylated NCP derivatives are chiral and congurationally stable, a feature that allows separation of isomers. Pure
enantiomers were nevertheless observed to racemize slowly
under acidic conditions. The interaction of 278.2 with chiral
acids and alcohols led to the formation of diastereomeric host
guest adducts, providing a potential NMR-based method of
quantifying enantiomer ratios. In subsequent work by Li, the
interaction between carbonyl-fused N-confused porphyrin
278.2b and bovine serum albumin (BSA) was investigated by
uorescence and UVvis spectroscopy. 1498 The results
indicated that 278.2b had an ability to quench the intrinsic
uorescence of BSA, and that the structure of BSA molecules
was changed by complexation with 278.2b.
7.6.3. Pentaphyrins. The N-fusion reaction is not limited
to NCP derivatives. In 2001, macrocycles 279.1 and 279.2, the
rst examples of N-fusion in a nonconfused expanded
porphyrin, were reported by the Osuka group (Scheme
279).1499 The two macrocycles, which dier in the length of
the macrocyclic conjugation circuit, were isolated in a direct
pyrrolebenzaldehyde condensation along with other ex-
Reagents and conditions:1495 (a) Re2(CO)10 (2 equiv), 1,2dichlorobenzene, 140 C, 16 h; (b) Re2(CO)10 (1 equiv), 1,2dichlorobenzene, 130 C, 24 h.
Condensation of 21-amino-substituted N-confused porphyrin 277.1 and benzaldehyde was found to produce isomeric
diazepine-fused inner-bridged porphyrinoids, 277.2a and
277.3a (Scheme 277).1496 Similar products were isolated in
the reactions with various p-substituted arylaldehydes. In the
absorption spectra, both 277.2a and 277.3a showed a similar
prole with the Q-like bands extending up to ca. 900 nm.
277.2a and 277.3a were found to interconvert in toluene-d8,
when heated at 381 K, 277.2a following rst-order kinetics. At
the equilibrium, the molar ratio of 277.2a and 277.3a was
around 4:1.
Li, Chmielewski, et al. reported that N-confused porphyrins
278.1ad reacted with paraformaldehyde under basic conditions, aording fused lactam derivatives 278.2ad containing
FY
Chemical Reviews
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Scheme 279. N-Fused Pentaphyrins and Their Reactivitya
Reagents and conditions: (a)1499 DDQ, CH2Cl2; (b)1499 NaBH4, MeOH, 10 min; (c)1501 [RhCl(CO)2]2, NaOAc, CH2Cl2; (d)1502 POCl3, NEt3,
toluene, 120 C, 12 h; (e)1502 Lawessons reagent, toluene, reux, 1 h; (f)1502 BH3SMe2, CH2Cl2, rt, 12 h; (g)1503 N-bromosuccinimide, pyridine,
CHCl3, reux; (h)1503 ammonium acetate, n-butylamine, or diethylamine, THF, reux; (i)1503 AcONaaq, THF, MeOH; (j)1503 BF3Et2O, NEt3,
toluene, 100 C.
Scheme 280. Synthesis of Doubly N-Fused Pentaphyrina
Reagents and conditions:1504 (a) (1) p-TSA, CH2Cl2, (2) DDQ, CH2Cl2; (b) DDQ, CH2Cl2; (c) CH2Cl2, rt, 2 days.
converted to the PS complex 279.6 by the action of

Lawessons reagent, whereas a reaction with BH3SMe2
produced the reduced phosphorus(III) complex 279.7 with a
hydrogenated bond. Compounds 279.5 and 279.6
exhibited strong 24-electron antiaromaticity, while the
complex 279.7 was found to be nonaromatic.
A complex transformation of the fused framework in 279.1
was reported by Suzuki, Hoshino, and Neya.1503 When treated
with NBS in reuxing pyridine, 279.1 underwent a skeletal
rearrangement, yielding the extensively fused product 279.9
(Scheme 279). Compound 279.9 showed an aromatic nature
derived from the 22-electron conjugation circuit and could be
aminated to produce a range of derivatives 279.8. Compound
279.10, obtained by solvolysis of 279.9, was shown to form a
boron complex 279.11, with a BF fragment bound in the
contracted cavity of the fused pentaphyrin.
In 2004, Furuta et al. demonstrated the synthesis of novel
doubly N-fused expanded porphyrin, pentaphyrin 280.5, which
proceeds via isomerization of the N-confusedN-fused
pentaphyrin 280.4 (Scheme 280).1504 Initially, the acidcatalyzed condensation of N-confused tripyrrane 280.1 and
the dipyrromethane dicarbinol 280.2 in the presence of ptoluenesulfonic acid (p-TSA), followed by oxidation with DDQ,
panded porphyrins. The yellow 24-electron species 279.1

could be quantitatively oxidized to the red, aromatic 22electron 279.2 with DDQ, and the transformation could be
reversed using NaBH4. The susceptibility to oxidation depends
on meso-substitution, and the CF3-substituted analogue of
279.1 was later found to be dicult to oxidize.1500 The
absorption spectra of both 279.1 and 279.2 displayed
signicant broadening, and a long-wavelength absorption
around 1000 nm was observed for the aromatic 279.2.1499 In
subsequent work, 279.2 was shown to form two mononuclear
rhodium(I) complexes, 279.3 and 279.4, diering in the metal
binding mode and the oxidation level of the macrocycle.1501
The 24-electron systems 279.3 adopted a Mobius-type
conformation and consequently exhibited a distinct diatropic
character.
Treatment of an N-fused [24]pentaphyrin 279.1 with a large
excess of POCl3 in the presence of triethylamine gave the triply
fused pentaphyrin phosphorus complex 279.5 through an Nfusion reaction of one of the C6F5 substituents combined with
the oxidative CC bond formation between two -pyrrolic
positions (Scheme 279).1502 The resulting heptacyclic fused
system contained an azepine ring fused to four dierently
oriented pyrroles. The phosphoryl complex 279.5 was
FZ
Chemical Reviews
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Scheme 282. Internally Bridged Hexaphyrinsa
resulted in the reduced form of N-confusedN-fused

pentaphyrin 280.3, which was further oxidized to produce the
22 aromatic 280.4. Pentaphyrin 279.4 proved to be quite
unstable and gradually isomerized to the doubly N-fused
porphyrinoid 280.5, containing a 24-electron conjugation
circuit. The electronic absorption spectrum of 280.5 showed
three broad bands between 300 and 800 nm, in line with the
antiaromatic character of the macrocycle. According to bond
resonance energy calculations, the main macrocyclic circuit in
the doubly N-fused core of 280.5 avoided all nitrogen atoms, as
indicated in Scheme 280. Using an analogous synthetic
approach, an N-confusedN-fused sapphyrin, 280.6, was
synthesized in one step from an N-confused pentapyrrane
precursor.1505 This compound formed alongside the corresponding nonfused N-confused sapphyrin, which could be
converted into 280.6 by treatment with NBS. 280.6 showed an
ability to form a ReI(CO)3 complex, analogous to 273.5;
however, in the case of the sapphyrin, the major metalation
product contained an additional ring formed by fusing one of
the meso-C6F5 substituents to the macrocycle.
7.6.4. Hexaphyrins. As shown above, N-fusion of adjacent
pyrrole subunits is the principal ring-forming process operative
in tetra- and pentaphyrins. In hexaphyrins and larger
porphyrinoids, meso-substitutent fusion becomes the dominant
reactivity route. Such a fusion involves nucleophilic substitution
at one ortho position of the meso substituent, either by a
neighboring pyrrolic nitrogen or by an oxygen nucleophile. The
former type of substitution was observed in 2002 by Hung and
co-workers in an Ullmann-type reaction of the antiaromatic
[28]trithiahexaphyrin 281.1 with CuCl in DMF (Scheme
281).1506 The resulting indole-fused system 281.2 contained a
Scheme 281. Ring Fusion in [28]Trithiahexaphyrina
Reagents and conditions:1511 (a) 125 equiv of BF3Et2O, O2, DCE/

NEt3, rt, 36 h; (b) NaBH4; (c) MnO2; (d)1507 toluene, pyridine, 90
C, 7 days; (e)1507 Pd(OAc)2, NaOAc, CH2Cl2, MeOH, rt, 12 h.
a
Reagents and conditions:1506 (a) CuCl, DMF, reux.
of Mobius aromatic metal-free expanded porphyrins, their

diatropicity being preserved even at 100 C, due to their
conformational rigidity (Scheme 282). Apparently, triethylamine was the source of all new carbons in 282.1ab. The
reduction of 282.1ab with NaBH4 caused a CN bond
cleavage, yielding a single [28]hexaphyrin 282.2, with a nearplanar conformation of the macrocyclic ring. The oxidation of
282.1ab with MnO2 resulted in a stereospecic CN bond
cleavage, producing [26]hexaphyrin enamines 282.3ab.
Excited-state decay dynamics of 282.2 and 282.3ab were
shown to be consistent with Huckel antiaromatic and Huckel
aromatic states, respectively.
7.6.5. Heptaphyrins. Heptaphyrin 283.1 underwent slow
but quantitative meso-substituent fusion to form the singly Nfused heptaphyrin 283.2 just on standing in solution (Scheme
283).1512 The conversion was observed in almost all solvents
examined except DMF, in which >95% of 283.1 was recovered
intact after standing for one month. Reuxing a toluene
solution of 283.2 for 12 h resulted in a quantitative formation
pyrrolo[1,2-a]indole fragment built into the hexaphyrin

macrocycle. An indole N-fused [28]hexaphyrin 282.4 was
obtained by heating 213.1 in a 5:1 mixture of toluene and
pyridine (Scheme 282).1507 The Mobius conformation in 282.4
was locked by metalation with Pd(OAc)2, which provided the
palladium(II) complex 282.5, with an enhanced aromatic
character. Further related contributions from the Osuka group
provided examples of singly and doubly indole-fused [28]hexaphyrins,1508 and SiIV hexaphyrin complexes containing
indole and benzopyran fusion.1509,1510
A distinct type of internal fusion was achieved in a reaction of
[26]hexaphyrin 213.1 with triethylamine in the presence of a
large excess of BF3Et2O and O2.1511 This complex addition
furnished a diastereomeric mixture of diethylamine-bearing
bridged [28]hexaphyrins 282.1ab, characterized by the
presence of two heterocyclic seven-membered rings, including
one fully conjugated azepine unit. 282.1ab are rare examples
GA
Chemical Reviews
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Scheme 283. Multiply N-Fused Heptaphyrinsa
Reagents and conditions:1512,1513 (a) solvent; (b) toluene, reux; (c) NaH, DMF, 60 C; (d) Cu(OAc)2, NEt3, CH2Cl2, MeOH, 25 C, 1 h.
of the doubly N-fused heptaphyrin 283.3. Further double Nfusion of 283.3 proceeded smoothly upon treatment with NaH
in DMF providing the quadruply N-fused heptaphyrin 283.4 in
71% yield. The proximate arrangement of the three pyrrole
units in 283.4 was found to stabilize tripyrrolylboron(III)
complexes, which displayed weak but distinct uorescence in
the near-infrared region. Treating heptaphyrin 283.4 with
copper(II) acetate produced the rst genuine T-shaped threecoordinate copper(II) complex 283.5.1513,1514
7.6.6. Other Porphyrinoids. As shown above, the N-fusion
reaction is a general process that could be induced in many
tetra- and pentaphyrins. The smallest system, in which N-fusion
was observed, is the contracted macrocycle 284.3, which
formed in low yield in the oxidative cyclization of a doubly Nconfused bilane 284.1, presumably with the intermediacy of the
N-confused N,C-linked corrole 284.2 (norrole, Scheme
284).1515 In solution, 284.3 exhibited a split Soret-like band
Scheme 285. Internally Fused Porphyrinoids via Subunit

Rearrangementa
Reagents and conditions: (a)1516 SnCl2, benzene, reux; (b)1517

AgOAc, CHCl3/CH3CN, reux.
Scheme 284. N-FusedN-Confused Norrolea
and pyrrolizin-5-one 285.5.1517 Both lactams were chiral and

could be separated into congurationally stable enantiomers.
7.7. peri-Fused Cyclophanes
7.7.1. peri-Fused Pyridine Cyclophanes. Drawing their

inspiration from the chemistry of both porphyrins and
cyclophanes, Ogawa and co-workers synthesized bis(phenanthroline) macrocycles 286.3 and 286.6 by direct
condensation of 2,9-dichloro-1,10-phenanthroline 286.2 with
diamino and dimethyl phenanthroline derivatives 286.1 and
286.5, respectively (Scheme 286).15181520 A simplied
procedure for the synthesis of 286.3, requiring only 286.2
and ammonia gas, was later reported by Wang et al.1521 286.3 is
a high-melting yellow solid that can be sublimed without
decomposition and is poorly soluble in common organic
solvents. In its principal tautomeric form, 286.3 is doubly
protonated on the inner nitrogens, as revealed by an XPS1522
and X-ray structural1521 analyses. In opposition to the early XPS
results, the X-ray structure revealed that the trans tautomer
prevails in the solid state, with localized positions of the inner
hydrogens. The corresponding peripherally protonated tautomer 286.4 was not observed experimentally, and the
preference for the inner protonation was rationalized by the
strong intramolecular hydrogen bonding that is possible in
286.3. In the dichloride salt, the dication [286.3]2+ was
proposed to be protonated on the external nitrogens.1520,1522
286.3 acts as a dibasic ligand, and its complexes with Cu(II),
Co(II), and Ni(II) were prepared by reactions of the
macrocycle with respective salts or by condensation of
Reagents and conditions:1515 (a) oxidant: DDQ, p-chloranil, ochloranil, or FeCl3.
(404 and 430 nm) in its absorption spectrum, accompanied by

a Q-like band at 606 nm. The compound was weakly
uorescent (F < 0.001) with a relatively large Stokes shift.
Unusual types of internal fusion are occasionally formed in
products of porphyrinoid rearrangements involving disruptions
of cyclic subunits. An example of such a process, reported by
Osuka and Furuta et al., is the conversion of corrorin 285.1,
the rst reported corrole isomer, into oxyindolophyrin 285.2,
induced by treatment with SnCl2 in reuxing benzene (Scheme
285).1516 285.2 is an aromatic species, with an [18]annulenoid
conjugation pathway available through a dipolar conjugation
contribution, and exhibited a porphyrin-like absorption
spectrum with an intense Soret band at 425 nm and Q bands
at 502 and 558 nm. The formyl-substituted [18]triphyrin(4.1.1)
derivative 285.3, obtained by Latos-Grazynski, Pawlicki, et al.,
was observed to undergo quantitative conversion into a mixture
of two uorescent lactams, the isomeric indolizin-5-one 285.4
GB
Chemical Reviews
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Scheme 286. Mono- and Bisphenanthroline peri-Fused Cyclophanes and Their Complexesa
a
Reagents and conditions: (a)1518 nitrobenzene, K2CO3, 94%; (b)1521 NH3 gas, 250 C, 8 h, 84% (as dichloride salt); (c)1520 neat, 260 C, 4 h, 94%;
(d)1534 ammonium acetate, EtOH, reux, overnight; (e)1535 Ni0(cod)2, cod, 2,2-bpy, toluene/DMF, 60 C.
substituted analogue, 286.14, by condensing diformylphenanthroline 286.13 with diethyloxaloacetate and ammonium
acetate.1534 This concise procedure is a specic application of
a more general synthesis of 2,5-di(2-pirydyl)pyrroles disclosed
by the same group.1534 286.14 revealed several interesting
characteristics, including cooperative amine binding, electrocatalytic and photosensitizing capabilities, and the formation of
lanthanide complexes. Torand-like cyclophenanthrolines
286.16ac, synthesized by Mullen and co-workers using a
Ni0-mediated cyclotrimerization of the respective dichlorophenanthrolines 286.15ac, were explored as self-assembling
neutral cation receptors1535 (for related phenanthrolineindole
hybrids lacking complete macrocyclic conjugation, see ref
1536). Binding of Na+, Ag+, and Pb2+ led to pronounced
changes in the absorption and emission characteristics of
286.16ac, with uorescence quenching being induced by Ag+
complexation. In the bulk, the complexes self-organized into
Colh phases, and it was observed that Ag+ and Pb2+ ions
induced a more ecient self-assembly. Ordered monolayers
formed on the HOPG surface for the complexes of 286.16b.
The lower packing density of these layers was ascribed to
electrostatic eects caused by the coordination of metal ions.
Fused heteroaromatic subunits are attractive building blocks
for the construction of diverse shape-persistent macrocycles. In
a remarkable example of early work, a rigid receptor 287.2 was
prepared by Cram and co-workers by Cu-mediated coupling of
the diiodo precursor 287.1 (Scheme 287).1537 287.2 was
initially isolated as a complex with CuCN, and the coordinated
CuI ion could only be removed by prolonged heating with
sodium cyanide. 287.2 was formed as the racemate, and the
corresponding meso form was not detected in the reaction
monophenanthrolines in the presence of a metal

source.1518,1519 Similar to its diaza analogue, compound 286.6
was also considered to favor the inner protonation, and the
prevalence of the dimethylene tautomer 286.7 was ruled out on
the basis of partial spectroscopic evidence. 286.6 is intensely
red in solution, in line with the extended conjugation present in
the major tautomer, and showed marked photosensitivity.1520
The sulfur-bridged bis-1,10-phenanthroline 286.8 was
prepared using various related strategies including the
nucleophilic cyclization of 286.2 with sulde sources.15231526
286.8 forms complexes with sodium, copper(I), and ruthenium,
which show various interactions with DNA.1524,1527,1528 A
related class of structures, 286.9 (M = Mn, Co, Ni, Cu; n = 2),
containing two imine bridges, were assembled by Anacona et
al., who condensed 286.1 with the respective dialdehyde in the
presence of appropriate metal chlorides.1529 The reaction did
not work with ZnII, PdII, and PtII ions, whereas the free base
286.9 (M = none, n = 0) could be obtained in 6070% yield by
direct condensation of the monophenanthrolines in the
presence of HCl or HCl/CrCl3. The templating eect of
metal ions in the synthesis of Schi base macrocycles, used to
prepare 286.9, was originally explored by Lewis and co-workers
(for comprehensive references, see ref 1529). The complexes
explored by these authors included several peri-fused
phenanthroline-based macrocycles of the general structures
286.10 and 286.11.15301532
A series of uorescent bis(phenanthrolinepyrrole) macrocycles 286.12ac was obtained by NorouziArasi, Mullen, et
al. by means of Suzuki-coupling cyclooligomerization.1533
WAXS studies showed that only 286.12b and 286.12c formed
liquid crystalline phases. Colbran et al. synthesized a dierently
GC
Chemical Reviews
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Scheme 287. Shape-Persistent Macrocycles Containing peri-Condensed Pyridine Ringsa
Reagents and conditions: (a)1537 (1) Cu bronze, biphenyl, reux, 20 min, (2) NaCN; (b) (1) NaCN, MeOH, H2O, reux, (2) MeOH, H2O, reux;
(c)1539 pyridine, KOH, 5570%.
condensed 1,7,13-triaza[18]annulenes 288.2 reported in 2002

by Meier et al. (Scheme 288).1542 These macrocycles, which
were obtained by cyclooligomerization of 288.1 in a Siegrist
reaction,1543 displayed pronounced photosensitivity, likely
associated with a cross-linking process. 288.2c formed a
mesophase in the 19157 C range (heating), which was
assumed to have the Colh structure analogous to that found in a
carbocyclic analogue of 288.2c.
Schmittel et al. used a two-component high-dilution
Sonogashira reaction to make the cyclic oligoacetylene
288.3.1544 This compound, which is characterized by the
presence of two exotopic phenanthroline binding sites, was
subsequently used for the assembly of a nanobox structure with
a void volume exceeding 5000 ,1545 as well as related
nanobaskets1546and nanotubes.1547 In a macrocyclic design by
Bauerle et al., an endotopic phenanthroline binding site was
used as a means of assembling oligothiophene catenanes such
as Cu(288.4)2(BF4).1548,1549 The ring-closing step used to
make the latter catenane and the parent monomacrocycle 288.4
involved the diiodine-induced extrusion of a platinum bridge.
Molecular modeling indicated that 288.4 and related systems
are strained and not completely planar.
Several macrocyclic systems are known in which peri-fused
pyridine-containing subunits are connected via hetero bridges.
Because of incomplete macrocyclic conjugation, these molecules are usually exible and often nonplanar. Macrocyclic triand tetraamides (C67.1 and C67.2, respectively), reported by
Huc et al.,1550 exhibit respectively near-planar and saddleshaped conformations (Chart 67). The trimeric species
assembles into tilted hydrogenhydrogen bonded stacks,
whereas C67.2 forms unusual rosette-like aggregates in the
solid state (Figure 6). In subsequent work, C67.1 was shown to
stabilize G-quadruplex DNA.1551 1,8-Naphthyridine oxacalixarenes of Katz et al. (e.g., C67.3) adopt nonplanar conformations
in the solid state and are capable of noncovalent dimerization
or binding of small guest molecules.1552 No structural data were
mixture. This stereoselectivity was proposed to originate from a

templating eect of the Cu ion during macrocyclization. Using
a similar cyclization strategy, Crams group prepared phenanthroline-based spherands 287.35.1538 With the smaller inner
substituents (R = Et), the stereoselective formation of the
racemate was again observed, whereas for R = i-Bu, the meso
form 287.5 was isolated in addition to the enantiomeric pair.
The structure of 287.3 was fully preorganized for cation
binding, and large free energies of formation were experimentally determined for a broad range of alkali metal and
ammonium cations. The preorganization is stereochemistrydependent and was not present in the 287.5 diastereomer.
A class of naphthyridine-based foldamers and macrocycles
was developed by Lehn and co-workers.1539 Their synthesis of
cyclotrimeric naphthyridines 287.7 is unique in that the nal
macrocyclization relied on the assembly of the heteroaromatic
subunits, rather than on the formation of intersubunit linkages
(Scheme 287). This cyclization strategy was very ecient, its
yields being limited mostly by isolation losses, and it did not
require high dilution conditions. Powder diraction data
obtained for 287.7 indicated that the rigid at cores of these
macrocycles form columnar stacks in the solid state. The
structural framework of 287.7 can be viewed as a macrocyclic
graphene substructure, a feature that results in a rigid, nearplanar conformation of the ring. Bis-phenanthroline systems
287.8 and 287.9, synthesized by Shionoya et al. using a Suzukicoupling cyclization,1540,1541 provide further examples of
graphenoid heteramacrocycles. 287.8 was explored as a
ligand for a range of metal ions (ZnII, AgI, CuI, LiI, MgII, PdII,
HgII, LaIII, TbIII), revealing a tendency to form heterodinuclear
complexes for certain ion pairs, such as AgI and CuI.1540 In
subsequent work, the dendronized derivative 287.9 as well as
its orthometalated bis-palladium complexes revealed an ability
to form one-dimensional brous aggregates, which were
characterized by means of scanning electron microscopy.1541
A perfect graphenoid framework is also found in the arenoGD
Chemical Reviews
Review
Scheme 288. Shape-Persistent Macrocycles Containing periCondensed Pyridine Ringsa
Figure 6. Rosette-like assemblies of C67.2 and chlorobenzene

molecules observed in the crystal. Reprinted with permission from
ref 1550. Copyright 2004 American Chemical Society.
provided for the Schi base macrocycle C67.4, reported by

Bhalla et al.1553 The macrocycle was shown to bind a variety of
metal ions, but the structural details of its coordination
chemistry were not disclosed.
7.7.2. peri-Fused Pyrrole Cyclophanes. Outside porphyrinoid chemistry, discussed in preceding sections, pyrrole
peri-fusion is most frequently encountered in carbazolophane
macrocycles. In this class of compounds, the tetraacetylene
macrocycle 289.3 has been the object of a particularly intense
exploration (Scheme 289). 289.3 was rst synthesized in 1999
by the group of Maruyama, who employed a macrocyclization
reaction between the bifunctional acyclic acetylenes 289.1 and
289.2.1554,1555 In addition to the cyclotetramer, the latter
reaction provided also the corresponding cyclooctameric
species 289.4, which was spectroscopically characterized.
Macrocycle 289.3 is apparently unstrained and can be
synthesized under equilibrium conditions using alkyne metathesis reactions. Moore et al. obtained 289.3 using their
precipitation-driven methodology (from 289.5),1556 via depolymerization-macrocyclization,1557 and by using silica supported
catalysts.1558,1559 Further synthetic methods include metathesis
reactions employing silyloxy-based catalysts of Furstner et
al.1560 and nitrilealkyne metathesis (from 289.6) by Johnson
et al.1561 The properties of 289.3 and its related derivatives
were explored in numerous applications, including nanobril
self-assembly,1562 explosives detection,15631565 chemiresistor
sensing of amines,1566,1567 surface assembly,1568 and solid-state
engineering.1569
Related diethynyl carbazole macrocycles, cyclotrimer 289.9
and cyclotetramer 289.10, were prepared by Zhu et al. using
Cu- or Cu/Pd-mediated acetylene couplings (Scheme 289).1570
To achieve satisfactory ring-size selectivity, these two macrocycles had to be prepared, respectively, from di- and
monocarbazole precursors (289.78). Photoinduced chargetransfer properties were studied for LangmuirBlodgett lms
of these macrocycles, which produced steady cathodic photocurrents (of up to 1.28 A cm2 for 289.9). A similar synthetic
strategy, employed by Osakada et al., produced the intramolecular coupling product 289.12, accompanied by the
nonplanar cyclodimer 289.13.1571 289.12 is moderately
strained (calculated H of 64.7 kJ/mol), but the associated
Reagents and conditions: (a)1542 t-BuOK, DMF.
Chart 67. Heteroatom-Bridged Pyridine-Containing

Cyclophanes
GE
Chemical Reviews
Review
Scheme 289. peri-Fused Carbazole-acetylene Macrocyclesa
Reagents and conditions: (a)1555 Pd(PPh3)4, CuI, THF, Et3N, rt; (b)1556 EtCMo[N(3,5-dimethylphenyl)(t-Bu)]3, p-nitrophenol, 30 C, 22 h,
CCl4; (c)1561 PhBr, 95 C; (d)1570 CuCl, CuCl2, pyridine, rt, 72 h; (e) Pd(PPh3)2Cl2, CuI, i-Pr2NH, THF, 50 C; (f)1571 Cu(OAc)2, pyridine/ether,
air, rt, 40 h.
a
benzylidenephosphoranes.15761578 Cyclic tetramers 290.11a

c and hexamer 290.12a were obtained using two- and onecomponent strategies. The two-component route involved the
direct condensation of dialdehydes 290.9 with diphosphonium
salts 290.10 and produced mainly cyclotetramers in yields up to
27%. A one-component route, employing the heterobifunctional dicarbazoles 290.13a proved more ecient, providing
improved yields of cyclotetramers and isolable quantities of
290.12a. The latter compound formed with unusual stereoselectivity, as an isomer with ve Z vinylene bridges. The sixth
bridge had an E conguration, yielding a buttery shaped threedimensionally folded structure, which persisted both in solution
and in the solid state.
Direct linking of carbazole units, analogous to that seen in
cyclopyrroles1213 and their derivatives, is a potentially
interesting way of creating large, shape-persistent macrocycles.
This concept was exploited by Mullen and co-workers who
synthesized the cyclododecameric nanoring 291.3.1579 To
improve the cyclization probability, a self-templating precursor
291.1 was rst prepared, in which four 2,2:7,2-tercarbazole
arms were attached to a tetraarylporphyrin core using exible
linkers (Scheme 291). These arms were subsequently joined
into the carbazolophane macrocycle 291.2, using a microwaveassisted Ni(0)-mediated coupling, which was performed at high
dilution (8 105 M) to minimize intermolecular coupling
reactions. The nal hydrolysis step released the free cyclocarbazole 291.3 in moderate yield. 291.3 assembles into 3D
columnar superstructures, investigated by means of 2D-WAXS
experiments. These structures have hexagonal symmetry and
intracolumnar helical order, and dier from conventional
distortion of carbazole and diethynyl subunits does not have a

signicant eect on the electronic properties of this system.
McMurry coupling has provided access to a range of
vinylene-bridged carbazolophanes. Compounds 290.1, obtained by Zhu and co-workers using direct cyclodimerization
of carbazole-3,6-dialdehydes (Scheme 290), showed improved
eld-eect transistor (FET) mobilities with respect to noncyclic
analogues, with 290.1b yielding a value of 0.013 cm2 V1
s1.1572 A similar cyclooligomerization reaction, performed on
the dialdehyde 290.9a by Step ien et al., produced a mixture of
the respective cyclodimer 290.2 and cyclotetramer
166.1.971,1573 Interestingly, 290.2 is formed stereoselectively
as the sterically more hindered syn isomer. Compound 166.1,
the precursor to chrysaorole 166.2 (section 6.1), was
alternatively obtained using a mixed WittigMcMurry protocol.
A related bromine-free cyclophane 290.3, synthesized under
analogous conditions, was used as a precursor to a carbazolebased molecular belt lacking complete peripheral conjugation.972 A range of large carbazolophanes containing various
embedded conjugated groups (290.48) was prepared by the
group of Rajakumar by cyclooligomerization of respective
dialdehydes.1574,1575 Compound 290.4, containing two isobenzotriazole units, showed uorescence quenching in the
presence of nitroaromatic analytes, showing a 19 ppm limit of
detection for picric acid.1575
Large vinylene carbazolophanes could be accessed using a
stereoselective variant of the Wittig reaction, described by
Step ien and co-workers (Scheme 290).1573 The synthetic
scheme relied on the anomalous Z-selectivity exhibited in
reactions of ortho-substituted arylaldehydes with semistabilized
GF
Chemical Reviews
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Scheme 290. peri-Fused CarbazoleVinylene Macrocyclesa
Yields of McMurry cyclooligomerizations are given for the top row. Reagents and conditions: (a,b)1573 aq NaOH (50%), DCM.
Scheme 291. Synthesis of [12]Cyclo(2,7)carbazolea
Reagents and conditions: (a)1579 Ni0(cod)2, 2,2-bipyridine, cod, toluene, DMF, 70100 C, 14 h; (b) KOH, H2O, MeOH, THF, reux, 24 h.
nanoring, so that a chemically accessible void is created in the

interior of the molecule. Using pulsed laser deposition, Mullen
and co-workers were able to ll the cavities with hexa-peribenzocoronene (HBC).1581 HBC molecules lled approximately 50% of the available voids and were seen to lie in the
same plane as the C68.1 macrocycles. A 2D WAXS study
performed on extruded bers of C68.1 revealed a liquid
crystalline Colh mesophase with the ahex lattice parameter of 5.4
nm.
discotic mesophases in the placement of alkyl chains, which

occupy the center of the column. An ecient charge transport
was predicted to occur in these columnar assemblies of these
macrocycles,1579 and was subsequently explored theoretically
using molecular dynamics simulations.1580
291.3 and the related acetylene macrocycle C68.11581 (Chart
68) both form uniform monolayers, with approximate
hexagonal packing, on the HOPG surface. In the case of
C68.1, alkyl chains are located principally on the outside of the
GG
Chemical Reviews
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Chart 68. Shape-Persistent Cyclic CarbazoleAcetylenes
Scheme 292. Synthesis of Carbazole-Based Nonclassical Nanotube End-capsa
Reagents and conditions: (a)1583 Ni0(cod)2, 2,2-bipyridine, DMF, 100 C, 24 h.
292.2 and 292.4 are uorescent, showing a complex dependence of their emission spectra on the axial conjugation length.
Cyclotrimerization of the azidoethynyl carbazole derivative
293.1 under [3+2] cycloaddition conditions was found by
Flood, Tait, et al. to provide the cyclotrimer 293.2 in very good
yield (Scheme 293).1584 This macrocycle showed high self-
The spoked-wheel macrocycle C68.2, investigated by the

groups of Hoger and Lupton as a model of extended
conjugation in polymeric systems, was synthesized by
templated Glaser-type cyclooligomerization around a covalently
bound rigid core of 6-fold symmetry (54% yield).1582 The
molecule of C68.2 has a diameter of 6 nm and is rigidied by
the presence of the fully conjugated core template. Singlemolecule uorescence of C68.2 was used to demonstrate
random localization of excitons and conrm their fundamentally nondeterministic character.
The self-templated macrocyclization paradigm was used by
Step ien and co-workers to synthesize nonclassical nanotube
end-caps 292.2 and 292.4 (Scheme 292).1583 292.2 can be
viewed as a capped [3]cyclo(2,7)carbazole, in which the
macrocyclic substructure forms a distinct tubular shape. 292.2
was obtained from the strain-free, nonmacrocyclic precursor
292.1, which was converted into the end-cap using a single Ni0mediated homocoupling reaction. The formation of 292.2
necessitates perfect synchronization of transmetalation and
reductive elimination (RE) steps. This synthetic method was
further extended to make 292.4, the benzo[def ]carbazole
analogue of 292.2; 292.2 and 292.4 contain the embedded
[6]cycloparaphenylene ([6]CPP) motif, and may be considered
heterocyclic analogues of small-diameter carbon nanotubes and
CPPs. The internal strain in 292.2 and 292.4, estimated using
a homodesmotic reaction scheme, is 138 and 144 kcal/mol,
respectively (B3LYP/6-31G(d,p)), signicantly higher than the
internal strain in [5]CPP. It was estimated using DFT
calculations that ca. 82% of the total internal strain is
introduced into 292.2 during the RE stage of macrocyclization.
Scheme 293. Synthesis of a Carbazole-Based Cyclophane via

[3+2] Cycloadditiona
Reagents and conditions: (a)1584 CuSO45H2O, sodium ascorbate,

TBTA, THF, EtOH, water, slow addition, 70 C.
a
association in solution and the ability to coordinate weak

anions, such as PF6, with positive cooperativity. Additionally,
hierarchically ordered tubes were observed to assemble from
molecules of 293.2 on graphite surfaces.
A family of donoracceptor segregated paracyclophanes was
developed by Takase et al. (Scheme 294).1585 The initial
macrocyclization was eected by a nucleophilic substitution
reaction between dipyrrolylbenzene 294.1 and hexauorobenGH
Chemical Reviews
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a]imidazoles furnished the respective hexaazacyclophanes

295.3.
7.7.3. Sulfur-Containing peri-Fused Cyclophanes. Even
though numerous sulfur-containing (mostly thiophenebased1587) cyclophanes are known, few of them actually
possess peri-fused rings. Apparently, the rst example of such
a structure, 8.2;8.2;8,2-tris(dibenzo[b,d]thiophenylene)
C69.1 (Chart 69), was reported in 1969 by Staab et al.1588
Their strategy of making C69.1, which relied on CuII-mediated
oxidative coupling of the Grignard reagent derived from 2,8dibromodibenzo[b,d]thiophene, could not be extended to the
synthesis of the dibenzofuran (X = O) and carbazole (X = NR)
analogues, presumably because of the higher internal strain of
the latter two targets. Another early example, 53.11, was
prepared by Boekelheide et al. as a precursor for the synthesis
of the fused thiophene 53.12 (see section 3.2).284 The
vinylene-linked bis(dibenzo[b,d]thiophenylene) C69.2, synthesized by Zhu et al. using McMurry cyclodimerization,1589 was
explored as a material for organic eld-eect transistors
(OFETs). In comparison with its nonmacrocyclic analogues,
C69.2 showed more favorable structural and charge-transport
characteristics, yielding a eld-eect hole-carrier mobility of
0.026 cm2 V1 s1. The groups of Rajakumar1590 and Muller1591
independently developed a family of phenothiazinophanes
(C69.35). C69.3 contains bent phenothiazine subunits and is
apparently conformationally restricted. The macrocycles show
electronic interactions between the redox-active subunits,
revealed by cyclic voltammetry, as well as moderately strong
uorescence with large Stokes shifts. Compound C69.6, a
structural analogue of C69.5 containing benzo[1,2-b:4,3b]dithiophene units, was reported by Bedi and Zade.1592 On
the Si/SiO2 surface, C69.6 showed self-assembly into bers of
ca. 400 nm diameter and lengths in the micrometer range.
McMurry coupling was also used by Lambert et al. to
synthesize thianthrenophane C69.7.1593 The cyclization was
low-yielding (3%), and the product was isolated as a racemic
mixture of the chiral D2-symmetric isomers. C69.7 revealed
exohedral coordination of AgI ions in the solid state, analogous
to that postulated for the free thianthrene, whereas the
formation of a 1:1 endohedral complex was postulated in
solution on the basis of UVvis titration data. C69.7 showed
an unusual carrier selectivity of silver(I), much higher than that
observed for thianthrene itself.
In hybrid macrocyclic systems, peri-fusion can be associated
not only with heterocyclic but also with carbocyclic subunits.
This fusion topology is exemplied by thiophenenaphthalene
cyclophane of Iyoda et al. (C69.8)1594 and acetylene-linked
hybrid thiophenetriphenylene macrocycles, developed by
Cammidge and co-workers (C69.911, cf., section 7.5).1595
Because of the restricted rotation of thiophene units, Iyodas
cyclophane can in principle form four distinct isomers, two of
which (C69.8a and C69.8b) were isolated from the reaction
mixture in a 5:1 ratio. C69.8a underwent both thermal and
photochemical isomerization to C69.8b. The redox and
emission properties of these cyclophanes indicated the eects
of face-to-face interaction of thiophenes and the deformation of
naphthalene units. The shape-persistent macrocycles C69.9
11, obtained by multistep protocols on the basis of acetylene
couplings, were designed as uorescent discotic liquidcrystalline materials. C69.9 and C69.10b formed discotic
nematic (ND) phases above 291 and 210 C, respectively,
whereas the remaining two systems were nonmesomorphic.
Scheme 294. Synthesis of DonorAcceptor Segregated

Paracyclophanesa
Reagents and conditions: (a)1585 C6F6, NaH, DMF/THF, 0 C, 40

min; (b) DDQ, Sc(OTf)3, DCM; (c) FeCl3, MeNO2/DCM.
zene, yielding the [2+2] condensation product 294.2

accompanied by the respective cyclotrimer. Subsequent
oxidative coupling of pairs of adjacent pyrrole rings yielded
the new macrocycle 294.3, containing peri-fused naphthobipyrrole subunits. The use of a stronger oxidant (FeCl3) enabled
intermolecular coupling of 294.3, which produced a moderate
yield of 294.4. The combination of electron donor and
acceptor moieties in 294.3 (naphthobipyrrole and tetrauorobenzene, respectively) was shown to result in electronic
transitions with a considerable charge-transfer character.
Abe, Nishiwaki, et al. showed that cyclohepta[4,5]pyrrolo[1,2-a]imidazoles of the general formula 295.1 undergo
cycloadditions with reactive acetylenes, yielding both [1+1]
and [2+2] addition products (Scheme 295).1586 The [2+2]
adducts 295.2 contained the [1,7]diaza[12]annulene ring and
had the ciscis conguration of the nonfused double bonds. An
analogous reaction performed on cyclohepta[d]imidazo[1,2Scheme 295. Heteraazulene-Based Cyclophanesa
Reagents and conditions: (a)1586 benzene or MeCN, reux, 1120 h,

343%.
GI
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Chart 69. Sulfur-Containing peri-Fused Macrocycles
7.7.4. Oxygen-Containing Cyclophanes. Two unusual

examples of oxygen-containing peri-fused cyclophanes are
found in synthetic natural product chemistry (Chart 70). The
threne macrocycles C70.3ab were synthesized by Luh and coworkers using a two-step cyclization approach involving
McMurry coupling and Mallorys photochemical cyclodehydrogenation.1598 A smaller ring, C70.4, was obtained in 2011 by
Nielsen et al. via nucleophilic cyclization of 6,6-diuoro-[1,1biphenyl]-2,2-diol.1599,1600
7.7.5. Heteroatom-Bridged Cyclophanes. The synthetic
chemistry of polycyclic arylamines, largely inspired by the
search for high-spin and mixed-valence organic molecules,1601
has produced a number of topologically nontrivial systems,
containing unusual peri-fusion patterns (Scheme 296). While
some of these molecules are highly nonplanar, they are of
general interest because of the extended -conjugation they
exhibit upon oxidation. An early example of such a system was
provided by Neugebauer and Kuhnhauser, who prepared the
double-decker triphenylamine 296.3 from the unstable
diazecine 296.1 in three steps.1602 296.3, prepared with the
intent of studying n() interactions, was proposed to retain the
planarity of the two amine bridges. The compound was very
sensitive to oxidation, forming a deep-violet radical cation. The
eld remained dormant until 1999 when the syntheses of nonperi-fused azacyclophanes 296.4 and 296.5 were reported by
the groups of Hartwig1603 and Tanaka.1604 Both groups used
the same cyclooligomerization strategy, relying on multiple
BuchwaldHartwig aminations, with cyclization yields apparently depending on peripheral substitution. In a parallel eort,
peri-fused naphthalene-containing analogues 296.8 and 296.9
were prepared by Selby and Blackstock, who used the classical
Ullmann amination conditions.1605 296.9 formed two stable
oxidation levels [296.9]+ and [296.9]2+, with the dication
Chart 70. Oxygen-Containing peri-Fused Macrocycles
completely conjugated macrocycles C70.1 were obtained by

Anjaneyulu et al. as products of Homan elimination
performed on Tiliacora racemosa akaloids.1596 Anhydrobartramiaavone C70.2, a macrocyclic bis(biluteolin), was
characterized by Geiger et al. as the product of acid-induced
dehydration of bartramiaavone, a biavonoid isolated from
Batramia pomiformis (apple moss).1597 Planar furanphenanGJ
Chemical Reviews
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Scheme 296. Polycyclic Arylamine Cyclophanesa
Reagents and conditions: (a)1602 (1) lithiation of 296.1, then addition of 296.2, 17%, (2) Raney Ni, H2, (3) diazotization in H3PO2, 8% (two
steps); (b)1603 Pd(OAc)2, P(t-Bu)3, t-BuONa, toluene, rt; (c)1604 [PdCl2(P(o-Tol)3)2], t-BuONa, toluene, 100 C, 16 h; (d)1605 Cu powder, K2CO3,
diphenyl ether, 190 C, 48 h; (e)1610 [Pd(dba)2], Q-Phos, t-BuONa, toluene, reux, 44 h; (f)1611 [Pd(dba)2], P(t-Bu)3, t-BuONa, toluene, reux, 19
h.
revealing a triplet ESR spectrum, with the D parameter of

0.0027 cm1.
Using the Pd-catalyzed amination strategy, Goodson,
Hartwig, et al. created ladder-like molecules 296.10 and
296.11.1606 In each case, the nal step involved the
incorporation of the outer phenylene rungs and gave yields
exceeding 80%. In cyclic voltammetry, these two systems
showed multiple overlapping oxidation events. When chemically oxidized with PIFA, 296.10 and 296.11 displayed a NIR
absorption band at ca. 1050 nm, corresponding to an
intervalence (IV) transition, associated with the coupling
between delocalized polarons and redox centers. Bis(metacyclophanes) 296.1214, structurally related to 296.10,
were subsequently reported by Wang and co-workers.1607
296.12, containing seven pyridine subunits, was explored as a

host for a range of divalent metal ions. Depending on the ionic
radius, the host was shown to coordinate either one or two
metal guests, and up to four binding modes were proposed on
the basis of available experimental data.
The groups of Ito and Tanaka succeeded in synthesizing a
variety of complex multicyclic topologies based on the
arylamine motif. Despite the generally low macrocyclization
yields, their strategies are highly step-ecient, as exemplied by
the syntheses of the planar tricycle 296.15 1608 and
pseudobeltane 296.16,1609 which involved the formation of 6
and 12 CN bonds, respectively, in the nal ring-closing step.
Up to 6 electrons could be removed electrochemically from
296.15, whereas spectroelectrochemical investigations revealed
GK
Chemical Reviews
Review
NIR absorptions up to the trication level, which experienced

noticeable blue shifts with the increasing oxidation level. 296.16
could be oxidized electrochemically up to the dodecacation
level, with the di- and tetracation exhibiting high spin states at
low temperature. Double- and triple-decker arylamines 296.19
and 296.21 were likewise obtained in one step from
nonmacrocyclic amines 296.17 and 296.20, respectively.1610
296.19 and 296.21 underwent electrochemical polymerization
during cyclovoltammetric studies. However, the reversible
multiredox behavior was restored in a derivative of 296.19
containing extended R groups. The extended triphenylamine
double-decker 296.24, reminiscent of 296.3, showed ve
chemically reversible oxidations in cyclic voltammetry.1611
The corresponding electronic spectra of the oxidized forms of
296.24 showed the blue-shift associated with the increasing
cationic charge.
In addition to the arylamine systems discussed above, a few
other heteroatom-bridged cyclophanes have been reported.
Allan and Podstata described the hexaaza[18]annulene
derivative 297.2, which was obtained in a stepwise fashion
using a sequence of diazo couplings.1612 The nal cyclization
step was presumably assisted by the network of intramolecular
hydrogen bonds, stabilizing the folded conformation of 297.1
(Scheme 297). A bis-quinazoline oxygen-bridged macrocycle
297.4, obtained by acid-catalyzed condensation of the amide
nitrile 297.3, was structurally characterized by Lindeman et
al.1613 Desroches et al. reported an untypical thermal route to
the thianthrene-containing cyclophane 297.8.1614 Their synthesis started with the formation of the tetra(O-thiocarbamoyl)
tetrathiacalixarene 297.6. The latter compound was subjected
to controlled heating in a DSC calorimeter revealing two
subsequent thermally induced reactions: the NewmanKwart
rearrangement to 297.6, occurring in the 270330 C range,
followed by the intramolecular cyclization to 297.8 above 380
C. 297.8 could be converted to a variety of isomeric sulfoxides,
such as 297.9,1615 some of which were subsequently explored
as cation receptors.1616
Scheme 297. Miscellaneous Heteroatom-Bridged

Cyclophanesa
a
Reagents and conditions: (a)1612 (1) NaNO2, HCl, (2) Na2CO3,
H2O; (b)1613 SOCl2, AlCl3, PhNO2; (c) Me2N(CS)Cl, Cs2CO3,
acetone, reux; (d) 290 C, 2 h; (e) 380410 C; (f)1615 HNO3 (0.14
M in CHCl3), rt, 30 min.
8. CONCLUSIONS AND OUTLOOK

As we have shown in this Review, the design and synthesis of
extended multiring frameworks is one of the key research
directions of modern heterocyclic chemistry. Even though the
rst polycyclic heteroaromatic molecules were synthesized over
one hundred years ago, the current state of the art has largely
been reached through the developments of the last two
decades, and provides a compelling illustration of the
remarkable recent progress in the synthesis of aromatic
compounds. Nevertheless, further renements of the existing
methodology are still needed to push the limits of attainable
molecular size, make systematic use of nonbenzenoid fusion,
increase heteroatom loading, and employ exotic elements in the
construction of new PHA systems.
The growth of the eld has been similarly stimulated by the
interest in fundamental properties of aromatic compounds and
by the prospective applications of -extended heterocycles.
Polycyclic heteroaromatics are arguably the most adaptable
class of organic molecules for use in postsilicon electronics,
oering nearly endless possibilities in molecular design. This
unique structural exibility can be used for programming
desirable features into PHA compounds at both molecular and
supramolecular levels. We anticipate that the rapidly broadening scope of available polycyclic heteroaromatics will help
develop rational structureproperty relationships, leading to

materials with precisely tunable characteristics.
AUTHOR INFORMATION
Corresponding Author
*E-mail: marcin.stepien@chem.uni.wroc.pl.
Notes
The authors declare no competing nancial interest.

Biographies
Marcin Step ien was born in 1977 in Wrocaw, Poland. He received his
Ph.D. in 2003 from the University of Wrocaw for his work on
porphyrinoid chemistry carried out with Professor Lechosaw LatosGrazynski. In 2005, he joined the group of Professor Jonathan L.
Sessler at the University of Texas to work on liquid-crystalline
expanded porphyrins. In 2010, he completed his habilitation at the
University of Wrocaw. Since 2015 he has been an associate professor
and a group leader at the same University. His research interests
include the synthesis, spectroscopy, and theory of nanographenes,
aromatic macrocycles, and highly strained organic molecules.
GL
Chemical Reviews
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DEAD
DFT
DIBAL-H
DIC
DMA
DMAD
DMAP
DME
DMF
DMSO
DNA
dppb
dppm
dppp
dtbpy
DPV
DS(SC)
DSC
ECL
ESIPT
ESR
EQE
Fc
FET
FT-IR
FVP
GIAO
GIXD
GNR
GQD
HBC, p-HBC
c-HBC
HMPA
HOMO
HOPG
HPHAC
HPLC
HREELS
Elzbieta Gonka was born in Poland in 1988. She received her M.Sc.
degree (2012) in chemistry from the University of Wrocaw, while
working in the group of Professor L. Latos-Grazynski. Since 2012 she
has performed doctoral work under the supervision of Professor
Marcin Step ien at the same University. In 2015, she received a
PRELUDIUM fellowship from the National Science Center of Poland.
Her research interest is focused on the bottom-up synthesis of
nitrogen-doped nanographenes.
Marika Z ya was born in 1990 in Nowa Ruda, Poland. She received her
M.Sc. degree (2014) in organic chemistry from the University of
Wrocaw. Currently, she is a doctoral candidate at the same University
under the guidance of Professor Marcin Step ien. Her research interests
are focused on the synthesis of new aromatic molecules, notably fused
oligopyrrolic compounds. In 2016, she received a PRELUDIUM
fellowship from the National Science Center of Poland.
Natasza Sprutta was born in 1972 in Wrocaw. She earned her Ph.D. in
2001 from the University of Wrocaw for her research on thiophenecontaining porphyrinoids carried out with Professor Lechosaw LatosGrazynski. She did her postdoctoral research in the group of Professor
Alan Balch at the University of California, Davis, working on heme
degradation models. She is currently working at the University of
Wrocaw, where she is exploring the chemistry of azulene-containing
macrocycles.
ACKNOWLEDGMENTS
Financial support from the National Science Center of Poland
(grants DEC-2012/07/E/ST5/00781 and DEC-2014/13/B/
ST5/04394 to M.S., and grant DEC-2014/15/N/ST5/00714
to E.G.) is gratefully acknowledged.
ABBREVIATIONS
ABCN
1,1-azobis(cyclohexanecarbonitrile)
Ac
acetyl
acac
acetylacetonate
AFM
atomic force microscopy
AICD
anisotropy of the induced current density
AIBN
azobis(isobutyronitrile)
Alq3
tris(8-hydroxyquinolinato)aluminum
AM
air mass (coecient)
BAHA
tris(4-bromophenyl)aminium hexachloroantimonate
BHJ
bulk heterojunction
BINAP
2,2-bis(diphenylphosphino)-1,1-binaphthyl
BODIPY
4,4-diuoro-4-bora-3a,4a-diaza-s-indacene
Bpin
4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl
bpy
2,2-bipyridyl
BSA
bovine cerum albumine
CAN
ceric ammonium nitrate
CD
circular dichroism
CIE
Commission International de lEclairage
cod
1,5-cyclooctadiene
Colh
columnar hexagonal (phase)
COT
cyclooctatetraene
m-CPBA
m-chloroperoxybenzoic acid
CPP
cycloparaphenylene
CT
charge transfer
CV
cyclic voltammetry
dba
trans,trans-dibenzylideneacetone
DBN
1,5-diazabicyclo[4.3.0]non-5-ene
DCE
1,2-dichloroethane
DCM
dichloromethane
DDQ
2,3-dichloro-5,6-dicyano-1,4-benzoquinone
HTC
ICT
IMFV
IVCT
Ir(ppy)3
ITO
LB
LC
LUMO
MALDI
MCD
MO
MSA
MW
NAP
NBS
NCP
NDI
NEXAFS
NFP
NHC
NICS
NIR
NIS
GM
diethyl azodicatboxylate
density functional theory
diisobutylaluminum hydride
dichloroisocyanuric acid
N,N-dimethylacetamide
dimethyl acetylenedicarboxylate
4-dimethylaminopyridine
dimethoxyethane
N,N-dimethylformamide
dimethylsufoxide
deoxyrybonucleic acid
1,1-bis(diphenylphosphino)butane
1,1-bis(diphenylphosphino)methane
1,1-bis(diphenylphosphino)propane
4,4-di-tert-butyl-2,2-bipyridyl
dierential pulse voltammetry
dye-sensitized (solar cell)
dierential scanning calorimetry
electrogenerated chemiluminescence
excited-state intramolecular proton transfer
electron spin resonance
external quantum eciency
ferrocene
eld-eect transistor
Fourier-transform infrared (spectroscopy)
ash vacuum pyrolysis
gauge-independent atomic orbital
grazing incidence X-ray diraction
graphene nanoribbon
graphene quantum dot
hexa-peri-benzocoronene
hexa-cata-benzocoronene
hexamethylphosphoramide
highest occupied molecular orbital
highly ordered pyrolytic graphite
hexapyrrolohexaazacoronene
high-performance liquid chromatography
high-resolution electron energy loss spectroscopy
hexathienocoronene
intramolecular charge transfer
internal molecular free volume
intervalence charge transfer transition
iridium(III) fac-tris(2-phenylpyridine)
indium tin oxide
LangmuirBlodgett (lms)
liquid crystal
lowest unoccupied molecular orbital
matrix-assisted laser desorption ionization
magnetic circular dichroism
molecular orbital
methanesulfonic acid
microwave (heating)
N-annulated perylene
N-bromosuccinimide
N-confused porphyrin
naphthalene diimide
near-edge X-ray absorption ne structure
N-fused porphyrin
N-heterocyclic carbene
nucleus-independent chemical shift
near-infrared
N-iodosuccinimide
Chemical Reviews
NLO
NMI
NMP
NMR
NPB
ODRC
OFET
OLED
OPA
OTFT
PAH
PCBM
PCE
PEDOT:PSS
PELDOR
PET
PHA
PHOLED
PIFA
PLD
PLED
POAV
PDI
PDT
PMI
PPA
PTFE
PVK
Q-Phos
RE
rt
SCE
SCLC
SPhos
SQUID
STM
SXR
SWCNT
TAPP
TAT
TBA(F,C,B)
TBTA
TCNE
TCNQ
TD-DFT
TEA
TEM
Tf
TFSIH
TFT
THF
TIPS
TFA
TMEDA
TMP
TOF
(p-)Tol
Review
TPA
TPD
TTF
TRISPHAT
nonlinear optics
naphthalene monoimide
N-methylpyrrolidone
nuclear magnetic resonance
1,4-bis(1-naphthylphenylamino) biphenyl
oxidative double-ring closure
organic eld-eect transistor
organic light-emitting diode
one-photon absorption
organic thin-lm transistor
polycyclic aromatic hydrocarbon
[6,6]-phenyl-C61-butyric acid methyl ester
(photovoltaic) power conversion eciency
poly(3,4-ethylenedioxythiophene) polystyrenesulfonate
pulsed electronelectron double resonance
photoinduced electron transfer
polycyclic heteroaromatic (system)
phosphorescent organic light emitting diode
phenyliodine bis(triuoroacetate)
pulsed laser deposition
polymer light-emitting diode
p-orbital axis vector
perylenediimide
photodynamic therapy
perylene monoimide
polyphosphoric acid
poly(tetrauoroethylene)
poly(9-vinylcarbazole)
pentaphenyl(di-tert-butylphosphino)ferrocene
reductive elimination
room temperature
standard calomel electrode
space-charge-limited current
2-dicyclohexylphosphino-2,6-dimethoxybiphenyl
superconducting quantum interference device
scanning tunneling microscope
specular X-ray reectivity
single-wall carbon nanotubes
1,3,8,10-tetraazaperopyrene
7,8,15,16-tetraazaterrylene
tetrabutylammonium (uoride, chloride, bromide)
tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine
tetracyanoethylene
tetracyanoquinodimethane
time-dependent DFT
triethylamine
transition electron microscopy
triuoromethanesulfonyl
(bis(triuoromethane)sulfonamide
thin-lm transistor
tetrahydrofuran
triisopropylsilyl
triuoroacetic acid
tetramethylethylenediamine
2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex (KnochelHauser
base)
time-of-ight
para-tolyl
TRMC
p-TSA
WAXS
XPS
XRD
two-photon absorption
temperature-programmed desorption
tetrathiafulvalene
tris(tetrachlorobenzenediolato) phosphate(V)
(anion)
time-resolved microwave conductivity
p-toluenesulfonic acid
wide-angle X-ray scattering
X-ray photoelectron spectroscopy
X-ray diraction
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Review

Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic

3.2. [ghi]Heteroannulated Perylenoids: 5-Membered Rings

Special Issue: Expanded, Contracted, and Isomeric Porphyrins

7.4.4. Fused 7-Membered Rings

The chemistry of heteroaromatic compounds is a vast

However, current production methods10,11 lead to random

Chart 1. Early Examples of Two-Dimensionally Fused

porphyrin analogues, and by advances in natural product

Figure 1. Research directions in modern PHA chemistry.

PHAs can be tailored into both p- and n-type semiconductors

This Review is focused on heteroaromatic systems in which the

by the presence of three-ring junctions (red dots, Chart 2),

Chart 3. Examples of peri-Condensed Frameworks Discussed in This Reviewa

Heteroatom placement and double bonds are not indicated.

authors. Related review articles are cited at the beginning of

unless the claims are of historical importance or have been

produced peri-fusion points or formed the heterocyclic

insucient analytical data and no follow-up work are usually

1.3. Classication and Nomenclature

Polycyclic heteroaromatic molecules presented in this Review

Scheme 2. Selected peri-Annulation Methods

pyrrole instead of isoindole), and are usually motivated by the

for this occasional inconvenience by providing relevant crossreferences.

1.4. Synthetic Strategies

As with any class of cyclic molecules, the major challenge in

that is, it involves the formation of a new ring via intramolecular

192.6) and numerous macrocyclization reactions (see section

40), sulfur, and selenium reagents (100.2, 107.11, 142.6,8,

137.10 for a tandem process involving an initial Heck-type

containing nitrogen or oxygen atoms are discussed in section

Rare examples of ring contractions, such as the extrusion of

2.1. Edge-Doped Aza- and Oxacoronenes

2.1.1. Diazacoronenes. The rst successful synthesis of

Chart 4. Classication of Coronenoids Used in This

-Conjugation and possible additional fused carbocyclic rings are not

Scheme 3. Synthesis of Diazacoronenes and Schi-Base Diazacoronenesa

Scheme 4. Synthetic Routes to Diimide Diazacoronenes and Thiophene Fused Azacoronenesa

photocyclization was used to produce thienoazacoronenes 4.7a

charge-carrier mobility were studied only for 3.11a/3.12a. Both

Scheme 5. Synthesis of Peripherally Functionalized

genations, yielding compounds 5.3ad and 5.6ac. These

1,2,4-triazoline-3,5-diones as dienophiles.7479 The utility of

Scheme 7. Synthesis of 1,5,9-Triazacoronenesa

Reagents and conditions: (a)68 aldehyde, DMF, 1% triic acid, 100

condensation of 8.1 and 8.2 apparently produced an

2.2. Pyrrole-Fused Azacoronenes

Hexapyrrolohexaazacoronene (HPHAC, Scheme 11) is the

Scheme 8. Synthetic Routes to Tetraazacoronene Derivativesa

Scheme 9. Synthetic Routes to 1,2,7,8-Tetraazacoronenes Containing N-Substituted 3,5-Dioxotriazoles Unitsa

Scheme 10. Synthetic Routes to 1,2,7,8-Tetrazazcoronene Polymersa

Jouini et al.82 11.2a was obtained as a soft homogeneous thin

presumably because of the low solubility of 11.2a in organic

Chart 5. Pyrrole-Fused Azacoronene Derivatives84

Scheme 11. Synthesis of Annularly Fused

Reagents and conditions: (a)80 Fe(ClO4)3, MeCN; (b)83 (1)

of the azacoronene core. Observation of uorescence and

Scheme 12. Synthetic Routes to Expanded Hexapyrrolohexaazacoronenesa

Scheme 13. Synthesis of a Peripherally Conjugated 5-6-7 Nanographenea

the doubly oxidized species [12.6]2+, a tendency toward

nate (BAHA) as the oxidant, led directly to a dicationic 5-6-7

Scheme 14. Synthesis of B-Doped Nanographenes and GNRsa

Ullmann-type step, performed by annealing the monomer