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Communication

pubs.acs.org/Organometallics

Coordination-Driven Self-Assembly of Fullerene-Functionalized Pt(II)


Metallacycles
Venkata S. Pavan K. Neti, Manik Lal Saha, Xuzhou Yan, Zhixuan Zhou, and Peter J. Stang*
Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States
S Supporting Information
*

ABSTRACT: We report the facile synthesis of C60 functionalized A2D2


(A = acceptor and D = donor) metallacycles M1 and M2, using the insight
from platinum(II)pyridine coordination driven self-assembly in combination with organo-fullerene chemistry. Both supramolecular adducts are
soluble in common organic solvents, which facilitates their structural
characterization by multinuclear NMR spectroscopy, UVvis spectroscopy, and electrospray ionization mass spectrometry.

Scheme 1. Self-Assembly of Fullerene-Functionalized


Metallacycles M1 and M2

ver the past two decades, a fascinating variety of discrete


metallosupramolecular architectures, with predesigned
shapes, sizes, and geometries, have been constructed, using the
coordination-driven self-assembly of rigid electron-poor metal
acceptors and complementary rigid electron-rich organic
donors.1,2 The covalent prefunctionalization of the precursor
units further enables the preparation of multif unctional
supramolecular assemblies in which the stoichiometry and
position of the individual functional moieties can be precisely
controlled. The latter have already proven their usefulness in a
wide range of applications, including highly selective
encapsulation, cavity-induced catalysis, and chemosensing.2
Fullerene-functionalized supramolecular architectures are
attractive for the preparation of advanced materials and for
the inhibition of HIV protease.3 Despite these remarkable
applications, such assemblies are still rare because of the poor
solubility of fullerene derivatives in most organic solvents,
which eventually causes serious characterization diculties for
the resultant complexes. This inadequacy has been partly
surmounted with the aid of organic functionalization of
fullerenes; thus, C60-based donors with mono- and hexaadducts have been used in coordination-driven self-assembly
processes.4
We herein combine the organo-fullerene chemistry with the
well-established platinum(II)pyridine coordination driven
self-assembly technique to report the syntheses and spectroscopic characterization of fullerene-based A2D2 (A = acceptor
and D = donor) metallacycles M1 (=[(3)2(1)2](NO3)4) and
M2 (=[(4)2(2)2](OTf)4) (Scheme 1 and Schemes S3 and S4 in
the Supporting Information). To the best of our knowledge,
M1 and M2 represent the rst monoadduct C60 functionalized
Pt(II) metallacycles.
2015 American Chemical Society

The fullerene-functionalized bispyridyl (120) and clip


(0) donors 1 and 2 (Scheme 1), respectively, were synthesized
in a two-step synthetic pathway from 3,5-dibromobenzaldehyde
(Schemes S1 and S2 in the Supporting Information). Thus,
palladium-catalyzed Sonogashira reactions between 3,5-dibromobenzaldehyde and 4-ethynylpyridine hydrochloride/3-ethynylpyridine were performed to obtain the bispyridyl donors 3,5bis(pyridin-4-ylethynyl)benzaldehyde and 3,5-bis(pyridin-3Received: August 20, 2015
Published: October 14, 2015
4813

DOI: 10.1021/acs.organomet.5b00718
Organometallics 2015, 34, 48134815

Communication

Organometallics

Figure S11 in the Supporting Information). The primary and


well-known monoadduct fulleropyrrolidine bands around 430
nm present in 1 and 2 and are also present in their
corresponding metallacycles. Other characteristic fullerene
bands at 260 and 330 nm are slightly red-shifted in the
metallacycles in comparison to the bands for the corresponding
fullerene donors.
In summary, we have described the synthesis of the two new
fulleropyrrolidines 1 and 2, bearing respectively bispyridyl
donors with 120 and 0 directionalities. These donor
precursors were successfully combined with their complementary diplatinum acceptors, providing the A2D2 coordination selfassemblies M1 and M2, as conrmed by multinuclear NMR
spectroscopy, UVvis spectroscopy, and electrospray ionization mass spectrometry.

ylethynyl)benzaldehyde. The aldehyde functionalities of these


ligands were further used in Prato reactions to furnish the
fulleropyrrolidine donors 1 and 2, in moderate yields.5
The 120 directing bispyridyl donor 1 was mixed with the
known 60 diplatinum acceptor 36 (1:1) in CD3SOCD3 and
stirred at room temperature for 24 h, thus leading to the
formation of rhomboidal metallacycle M1 (=[(3)2(1)2]
(NO3)4) (Scheme 1). Similarly, using the clip donor 2 and
the 180 organoplatinum(II) acceptor 46 in a 1:1 ratio, we
prepared the fullerene-functionalized metallacycle M2
(=[(4)2(2)2](OTf)4) (Scheme 1).
The A2D2 compositions of M1 and M2 were established by
electrospray ionization time-of-ight mass spectrometry
(ESITOF-MS). In the mass spectrum of M1 three peaks, at
m/z 2156.50 for [M 2ONO2]2+, m/z 1416.97 for [M
3ONO2]3+, and m/z 1047.23 for [M 4ONO2]4+ (where M =
intact assembly), were observed, which are consistent with the
A2D2 structural assignment (Figure S5 in the Supporting
Information). Similarly, for M2, one peak was found at m/z
2143.79, corresponding to [M 2OTf]2+ (Figure S6 in the
Supporting Information). All these peaks matched well with
their calculated theoretical isotope distributions (Figure S7 in
the Supporting Information).
The 1H and 31P{1H} NMR of M1 and M2 revealed similar
features that are consistent with the formation of the proposed
assemblies. For example, the 31P{1H} NMR spectra of M1 and
M2 showed sharp singlets at 7.3 and 12.5 ppm, respectively,
indicative of a single phosphorus environment, as expected
(Figure 1). The peaks of M1 and M2 were shifted upeld from

ASSOCIATED CONTENT

S Supporting Information
*

The Supporting Information is available free of charge on the


ACS Publications website at DOI: 10.1021/acs.organomet.5b00718.
Synthetic procedures and NMR and mass spectra for all
new compounds (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail for P.J.S.: stang@chem.utah.edu.


Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
P.J.S. thanks the NSF (1212799) for nancial support.
REFERENCES

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Figure 1. 31P{1H} NMR spectra (room temperature, 121.4 MHz) of


(a) 3, (b) M1, (c) 4, and (d) M2.

the starting platinum acceptors 3 ( 18.1 ppm) and 4 ( 19.0


ppm). This change and the decrease in coupling of the anking
195
Pt satellites (ca. J = 186 Hz for M1 and J = 124 Hz
for M2; Figure 1) are consistent with back-donation from the
platinum atoms.
Likewise in the 1H NMR spectra of M1 and M2, the
resonances for the a and b protons (Scheme 1) of the pyridyl
groups as well as the pyrrolidine protons (e.g., p-H) exhibited
downeld shifts as compared to those observed in the free
ligands 1 and 2 (see Figures S8S10 in the Supporting
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The UVvis spectra of ligands 1 and 2 and of M1 and M2
showed several absorption bands between 230 and 450 nm (see
4814

DOI: 10.1021/acs.organomet.5b00718
Organometallics 2015, 34, 48134815

Communication

Organometallics
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DOI: 10.1021/acs.organomet.5b00718
Organometallics 2015, 34, 48134815

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