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Stacking of conical molecules with a fullerene apex into polar columns in crystals and liquid crystals

Abstract

Polar liquid crystalline materials can be used in optical and electronic applications, and recent interest has turned to formation strategies that exploit the shape of polar molecules and their interactions to direct molecular alignment1,2. For example, banana-shaped molecules align their molecular bent within smectic layers3, whereas conical molecules should form polar columnar assemblies4,5,6,7,8,9. However, the flatness of the conical molecules used until now4,5,6,9 and their ability to flip7,8 have limited the success of this approach to making polar liquid crystalline materials. Here we show that the attachment of five aromatic groups to one pentagon of a C60 fullerene molecule yields deeply conical molecules that stack into polar columnar assemblies. The stacking is driven by attractive interactions between the spherical fullerene moiety and the hollow cone formed by the five aromatic side groups of a neighbouring molecule in the same column. This packing pattern is maintained when we extend the aromatic groups by attaching flexible aliphatic chains, which yields compounds with thermotropic and lyotropic liquid crystalline properties. In contrast, the previously reported fullerene-containing liquid crystals10,11,12,13,14,15,16,17 all exhibit thermotropic properties only, and none of them contains the fullerene moiety as a functional part of its mesogen units. Our design strategy should be applicable to other molecules and yield a range of new polar liquid crystalline materials.

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Figure 1: Fullerene derivatives with deeply conical structures.
Figure 2: Crystal packing of biphenyl compound 1.
Figure 3: Crystalline and liquid crystalline properties and structures of 15.
Figure 4: SAXD patterns of liquid crystals of 25.

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Acknowledgements

We thank Frontier Carbon Corporation for generous supply of C60. The present research was supported by a Grant-in-Aid for Scientific Research (Specially Promoted Research) from the Ministry of Education, Culture, Sports, Science, and Technology.

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Correspondence to Eiichi Nakamura.

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Sawamura, M., Kawai, K., Matsuo, Y. et al. Stacking of conical molecules with a fullerene apex into polar columns in crystals and liquid crystals. Nature 419, 702–705 (2002). https://doi.org/10.1038/nature01110

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