2009-2010

Encaging the Light

Research Report
Erasmus Internship in SMCT (SupraMolecular Chemistry &
Technology), Faculty of Science and Technology (TNW),
University of Twente.

Synthesis and
Photophysical
Study of Caged
Iridium
Complexes

Miguel Berenguel Alonso

Supervisors
UAB Coordinator

Albert Ruggi, M. Sc.

Dr. Aldrik H. Velders
Dr. Jordi Hernando

Encaging the Light

Synthesis and Photophysical Study of Caged Iridium Complexes
Miguel Berenguel Alonso

SupraMolecular Chemistry & Technology

Faculty of Science and Technology TNW
University of Twente
Enschede, The Netherlands

Departament de Qumica
Universitat Autnoma de Barcelona
Bellaterra (BCN), Spain

University of Twente
MESA+ Institute for Nanotechnology
SMCT Supramolecular Chemistry & Technology

ii

Encaging the Light

Synthesis and Photophysical Study of Caged Iridium Complexes
Miguel Berenguel Alonso

Abstract
Iridium(III) complexes have attracted great interest during the last years due to their
outstanding luminescence properties, such as high emission intensities, long lifetimes in the
range of s, and color tunability so as to cover a full range of visible colors. These properties
result in a wide field of potential applications.
Nevertheless, Iridium(III) cyclometallated complexes, like other
metal complexes, present a strong oxygen quenching of their
luminescence, which is a serious drawback in most applications.
The research work presented in this thesis concerns with the
synthesis, characterization and study of the photophysical
behavior of the first caged-Iridium(III) complex (see Figure 1).
We proved that this complex shows a reduced oxygen
quenching (80%), probably caused by the shielding provided by
the ligand structure towards the excited state orbitals (see
Section 4.1).
Furthermore, three other approaches to the synthesis of
different caged-Iridium(III) complexes are reported.

Figure 1 First Iridium(III) Cagedcomplex.

The

Figure 2 Structures of the three other target Iridium(III) caged-complexes.

University of Twente
MESA+ Institute for Nanotechnology
SMCT Supramolecular Chemistry & Technology

iii

Encaging the Light

Synthesis and Photophysical Study of Caged Iridium Complexes
Miguel Berenguel Alonso
structures of the target caged-complexes (Sections 4.2, 4.3 and 4.4, respectively) are displayed
in Figure 2. The amine-based trivalent scaffold is substituted with a benzene ring, which is
more bulky than the amine-based one and, a priori, more rigid. Two of the target complexes
(14 and 19) have not been completely syntheiszed due to the complexity of the synthesis and a
lack of time. Nevertheless, an advanced intermediate (tripodal ligand) of the last structure was
already synthesized, as well as two reference compounds, needed for the comparison of the
photophysical properties. The target complex 9 had to be discarded due to insurmountable
synthetic problems.

University of Twente
MESA+ Institute for Nanotechnology
SMCT Supramolecular Chemistry & Technology

iv

Encaging the Light

Synthesis and Photophysical Study of Caged Iridium Complexes
Miguel Berenguel Alonso

Table of Contents
Abstract ................................................................................................. iii
Table of Contents .................................................................................... v
Abbreviations ....................................................................................... viii
1.

Introduction ................................................................................... 2

1.1.

General Introduction.............................................................................................. 3

1.2.

Interaction of light with molecules ........................................................................ 4

1.2.1.
1.2.1.1.
1.2.1.2.

Absorption, Excited State and Emission .................................................................... 6

Absorption .......................................................................................................................... 7
Emission ............................................................................................................................. 9

1.2.2.

Important Parameters ............................................................................................. 10

1.2.3.

Differences between Organic Molecules and Metal Complexes ............................ 11

1.2.4.

Luminescence in Transition Metal Complexes ........................................................ 12

1.2.5.

Quenching ............................................................................................................... 14

1.2.5.1.
1.2.5.2.

1.3.

Static Quenching .............................................................................................................. 14

Dynamic or Collisional Quenching.................................................................................... 15

Iridium(III) Cyclometalated Complexes ................................................................ 17

1.3.1.

Structure and Synthesis........................................................................................... 17

1.3.2.

Photophysical Properties of Cyclometalated Iridium(III) Complexes ..................... 19

1.3.3.

Applications ............................................................................................................. 21

1.3.3.1.
1.3.3.2.
1.3.3.3.

1.3.4.

OLED Applications ............................................................................................................ 21

Oxygen Sensor Applications ............................................................................................. 22
Other Applications ........................................................................................................... 23

Caged Complexes .................................................................................................... 24

1.4.

References ........................................................................................................... 25

2.

Aims of the work .......................................................................... 28

3.

Experimental Section .................................................................... 30

3.1.

General ................................................................................................................ 31

3.2.

Materials.............................................................................................................. 32
University of Twente
MESA+ Institute for Nanotechnology
SMCT Supramolecular Chemistry & Technology

Encaging the Light

Synthesis and Photophysical Study of Caged Iridium Complexes
Miguel Berenguel Alonso

3.3.

Synthesis .............................................................................................................. 32

3.3.1.

Structure A .............................................................................................................. 32

3.3.2.

Structure B............................................................................................................... 36

3.3.3.

Structure C............................................................................................................... 36

3.3.4.

Structure D .............................................................................................................. 37

3.3.4.1.
3.3.4.2.
3.3.4.3.
3.3.4.4.

Tactic 1 ............................................................................................................................. 37
Tactic 2 (Failed) ................................................................................................................ 38
Reference Open Complex................................................................................................. 39
Reference Hemicaged-Complex ....................................................................................... 40

3.4.

References ........................................................................................................... 41

4.

Results and Discussion .................................................................. 42

4.1.

Structure A ........................................................................................................... 45
4.1.1.
Synthesis of Ir Caged-Complex 4 ...................................................................................... 45
4.1.1.1. Step 1. Methylation of the acid group ......................................................................... 46
4.1.1.2. Step 2. Suzuki Coupling ................................................................................................ 47
4.1.1.3. Step 3. DCC/HOBt Coupling ......................................................................................... 47
4.1.1.4. Step 4. Iridium Complexation ...................................................................................... 48
4.1.1.5. Step 5. MethylEster Deprotection and Cage Closure................................................... 49

4.1.2.

Structural Determination ........................................................................................ 50

4.1.3.

Photophysics ........................................................................................................... 53

4.1.3.1.
4.1.3.2.
4.1.3.3.

UV/Visible Absorption ...................................................................................................... 53

Emission ........................................................................................................................... 54
Quenching ........................................................................................................................ 55

4.2.

Structure B ........................................................................................................... 57

4.3.

Structure C ........................................................................................................... 59

4.4.

Structure D ........................................................................................................... 61

4.4.1.

Caged-complex ........................................................................................................ 62

4.4.2.

Reference Complexes .............................................................................................. 65

4.5.

References ........................................................................................................... 67

5.

Outlook ........................................................................................ 69

5.1.

Conclusions .......................................................................................................... 70

5.2.

Future Work ......................................................................................................... 70

5.3.

Personal Considerations ...................................................................................... 71

University of Twente
MESA+ Institute for Nanotechnology
SMCT Supramolecular Chemistry & Technology

vi

Encaging the Light

Synthesis and Photophysical Study of Caged Iridium Complexes
Miguel Berenguel Alonso

6.

Acknowledgments ........................................................................ 72

7.

Appendix ...................................................................................... 74

7.1.

Reaction Mechanisms .......................................................................................... 75

7.1.1.

Methylation of Carboxylic Acid ............................................................................... 75

7.1.2.

Suzuki Coupling ....................................................................................................... 76

7.1.3.

DCC/HOBt coupling ................................................................................................. 78

7.1.4.

Click Reaction Huisgen 1,3-Dipolar Cycloaddition .................................................. 79

7.2.

NMR and Mass Spectra ....................................................................................... 80

7.2.1.

Structure A .............................................................................................................. 81

7.2.1.1.
7.2.1.2.
7.2.1.3.
7.2.1.4.

7.2.2.

4-(5-(methoxycarbonyl)pyridin-2-yl)benzoic acid (1) ....................................................... 81

Tripodal ligand (2) ............................................................................................................ 83
Hemicaged Iridium complex (3) ....................................................................................... 85
Caged Iridium complex (4) ............................................................................................... 88

Structure B............................................................................................................... 89

7.2.2.1.

7.2.3.

2-(4-methoxy-phenyl)-5-methyl-pyridine (5) ................................................................... 89

Structure C............................................................................................................... 91

7.2.3.1.
7.2.3.2.
7.2.3.3.

7.2.4.

2,2',2''-(benzene-1,3,5-triyl)triethanol (10) ..................................................................... 91

1,3,5-tris(2-iodoethyl)benzene (11) ................................................................................. 92
Tripodal ligand (12) .......................................................................................................... 93

Structure D .............................................................................................................. 94

7.2.4.1.
7.2.4.2.
7.2.4.3.
7.2.4.4.
7.2.4.5.
7.2.4.6.
7.2.4.7.
7.2.4.8.
7.2.4.9.
7.2.4.10.
7.2.4.11.

7.3.

6-bromopyridin-3-ol (15) ................................................................................................. 94

1,3,5-tris(((6-bromopyridin-3-yl)oxy)methyl)benzene (16).............................................. 95
Tripodal Ligand (17).......................................................................................................... 96
6-(4-(benzyloxy)phenyl)pyridin-3-ol (20) ......................................................................... 98
6-(4-(benzyloxy)phenyl)pyridin-3-yl pivalate (21) .......................................................... 100
6-(4-hydroxyphenyl)pyridin-3-yl pivalate (22) ............................................................... 102
6-(4-hydroxyphenyl)pyridin-3-ol (24) ............................................................................. 104
5-methoxy-2-(4-methoxyphenyl)pyridine (25) .............................................................. 105
Iridium Open Complex (26) ............................................................................................ 107
Tripodal ligand (27) .................................................................................................... 110
Iridium Hemicaged Complex (28) .............................................................................. 113

References ......................................................................................................... 115

University of Twente
MESA+ Institute for Nanotechnology
SMCT Supramolecular Chemistry & Technology

vii

Encaging the Light

Synthesis and Photophysical Study of Caged Iridium Complexes
Miguel Berenguel Alonso

Abbreviations
DFT
ESI-MS

Density-Functional Theory
Electrospray Ionization Mass Spectrometry

fac

facial

FT-IR
HOMO
ITO
LC
LMCT
LUMO
MALDI-MS
MC
mer
MLCT
MO
OLED
RT
S0
Sn
str
T1
TLC
UV

Fourier Transform Infrared Spectroscopy

Highest Occupied Molecular Orbital
Indium Tin Oxide
Ligand Centered
Ligand-to-Metal Charge Transfer
Lowest Unoccupied Molecular Orbital
Matrix-Assisted Laser Desorption Ionization Mass Spectrometry
Metal Centered
meridional
Metal-to-Ligand Charge Transfer
Molecular Orbital
Organic Light-Emmiting Device
Room Temperature
Singlet ground state
Singlet n-excited state
Stretching
Triplet first-excited state
Thin Layer Chromatography
Ultraviolet

Chemical Structures
-NPD
acac
Alq3
BCP
BHT
bpy
DCC

4,4-bis-[N-(naphthyl-N-phenylamino)biphenyl
Monoanion of acetyl acetone
tri-(8-hydroxyquinoline) aluminum(III)
2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
Butylated hydroxytoluene
2,2'-bipyridine
N,N'-dicyclohexylcarbodiimede

DMA

N,N-dimethylacetamide

DMF
DMSO
dpm
HOBt

N,N-dimethylformamide
Dimethylsulfoxide
Monoanion of 2,2,6,6-tetramethyl-3,5-heptanedione
Hydroxybenzotriazole
University of Twente
MESA+ Institute for Nanotechnology
SMCT Supramolecular Chemistry & Technology

viii

Encaging the Light

Synthesis and Photophysical Study of Caged Iridium Complexes
Miguel Berenguel Alonso
LDA
LiTMP
ppy
TBAB
TBAF
TBDMS
TFA
THF
Tren

Lithium diisopropylamide
Lithium 2,2,6,6-tetramethylpiperidide
Monoanion of 2'-phenylpyridine
Tetrabuthyl amonium bromide
Tetrabuthyl amonium fluoride
tert-buthyldimethylsilyl
Trifluoroacetic acid
Tetrahydrofuran
Tris(2-aminoethyl)amine

Nuclear Magnetic Resonance

13

Carbon-13 Nuclear Magnetic Resonance

Hydrogen-1 Nuclear Magnetic Resonance

Broad
Correlation Spectroscopy
Doublet
Heteronuclear Multiple Bond Correlation
Heteronuclear Multiple Quantum Coherence
Multyplet
Nuclear Overhauser Effect
Rotational Frame Nuclear Overhauser Effect
Spectroscopy
Singlet
Triplet

C NMR

H NMR
br
COSY
d
HMBC
HMQC
m
NOE
ROESY
s
t

University of Twente
MESA+ Institute for Nanotechnology
SMCT Supramolecular Chemistry & Technology

ix