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A grossly warped nanographene and the consequences of multiple odd-membered-ring defects

Nature Chemistry volume 5, pages 739–744 (2013)Cite this article

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Abstract

Graphite, the most stable form of elemental carbon, consists of pure carbon sheets stacked upon one another like reams of paper. Individual sheets, known as graphene, prefer planar geometries as a consequence of the hexagonal honeycomb-like arrangements of trigonal carbon atoms that comprise their two-dimensional networks. Defects in the form of non-hexagonal rings in such networks cause distortions away from planarity. Herein we report an extreme example of this phenomenon. A 26-ring C80H30 nanographene that incorporates five seven-membered rings and one five-membered ring embedded in a hexagonal lattice was synthesized by stepwise chemical methods, isolated, purified and fully characterized spectroscopically. Its grossly warped structure was revealed by single-crystal X-ray crystallography. An independent synthetic route to a freely soluble derivative of this new type of ‘nanocarbon’ is also reported. Experimental data reveal how the properties of such a large graphene subunit are affected by multiple odd-membered-ring defects.

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Figure 1: Structure of 4, its salient properties and three different synthesis methods.
Figure 2: ORTEP images showing the warped structure of the new C80H30 nanographene 4, taken from the X-ray crystal structure.
Figure 3: Conformational flexibility of the grossly warped C80H30 nanographene.
Figure 4: Optical properties of the grossly warped C80H30 nanographene (4) compared to those of a planar PAH of similar size.

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Acknowledgements

K.K. thanks the Japan Society for the Promotion of Science (JSPS) and the Nagoya University Global Center of Excellence Program for fellowships. This research was supported financially by the US National Science Foundation (L.T.S.) and the Funding Program for Next Generation World-Leading Researchers from JSPS (K.I.). We thank Mr T. Fujikawa for conducting the reactions of [6]helicene. K. Tatsumi and Y. Ohki are greatly acknowledged for providing access to their X-ray analysis instruments. We thank S. Yamaguchi, A. Fukazawa and S. Saito for assistance in the photophysical measurements. S. Seki and A. Saeki are acknowledged for measurements and discussion. Calculations were performed using the resources of the Research Center for Computational Science, Okazaki, Japan.

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Authors and Affiliations

  1. Department of Chemistry, Graduate School of Science, Nagoya University, Chikusa, 464-8602, Nagoya, Japan

    Katsuaki Kawasumi, Yasutomo Segawa & Kenichiro Itami

  2. Merkert Chemistry Center, Boston College, Chestnut Hill, 02467-3860, Massachusetts, USA

    Qianyan Zhang & Lawrence T. Scott

  3. Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, 464-8602, Nagoya, Japan

    Kenichiro Itami

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  1. Katsuaki Kawasumi
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Contributions

K.K. and Q.Z conducted the experiments. Y.S. performed the X-ray crystal structure analysis and DFT calculations. L.T.S. and K.I. conceived the concept and prepared the manuscript with feedback from others.

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Correspondence to Lawrence T. Scott or Kenichiro Itami.

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Crystallographic data for compound 4 (CIF 46 kb)

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Kawasumi, K., Zhang, Q., Segawa, Y. et al. A grossly warped nanographene and the consequences of multiple odd-membered-ring defects. Nature Chem 5, 739–744 (2013). https://doi.org/10.1038/nchem.1704

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