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.

References

  1. 1

    Guillon, D. Molecular engineering for ferroelectricity in liquid crystals. Adv. Chem. Phys. 113, 1–49 (2000)

    CAS  Google Scholar 

  2. 2

    Kato, T. Self-assembly of phase-segregated liquid crystal structures. Science 295, 2414–2418 (2002)

    ADS  CAS  Article  Google Scholar 

  3. 3

    Niori, T., Sekine, T., Watanabe, J., Furukawa, T. & Takezoe, H. Distinct ferroelectric smectic liquid crystals consisting of banana shaped achiral molecules. J. Mater. Chem. 6, 1231–1233 (1996)

    CAS  Article  Google Scholar 

  4. 4

    Cometti, G., Dalcanale, E., Du Vosel, A. & Levelut, A.-M. New bowl-shaped columnar liquid crystals. J. Chem. Soc. Chem. Commun. 163–165 (1990)

  5. 5

    Xu, B. & Swager, T. M. Rigid bowlic liquid crystals based on tungsten-oxo calix[4]arenes: host-guest effects and head-to-tail organization. J. Am. Chem. Soc. 115, 1159–1160 (1993)

    CAS  Article  Google Scholar 

  6. 6

    Komori, T. & Shinkai, S. Novel columnar liquid crystals designed from cone-shaped calix[4]arenes. The rigid bowl is essential for the formation of the liquid crystal phase. Chem. Lett. 1455–1458 (1993)

  7. 7

    Malthête, J. & Collet, A. Liquid crystals with a cone-shaped cyclotriveratrylene core. Nouv. J. Chim. 9, 151–153 (1985)

    Google Scholar 

  8. 8

    Malthête, J. & Collet, A. Inversion of the cyclotribenzylene cone in a columnar mesophase: a potential way to ferroelectric materials. J. Am. Chem. Soc. 109, 7544–7545 (1987)

    Article  Google Scholar 

  9. 9

    Kang, S. H. et al. Novel columnar mesogen with octupolar optical nonlinearities: synthesis, mesogenic behaviour and multiphoton-fluorescence-free hyperpolarizabilities of subphthalocyanines with long aliphatic chains. Chem. Commun. 1661–1662 (1999)

  10. 10

    Chuard, T. & Deschenaux, R. First fullerene[60]-containing thermotropic liquid crystal. Helv. Chim. Acta 79, 736–741 (1996)

    CAS  Article  Google Scholar 

  11. 11

    Chuard, T., Deschenaux, R., Hirsch, A. & Schönberger, H. A liquid-crystalline hexa-adduct of [60]fullerene. Chem. Commun. 2103–2104 (1999)

  12. 12

    Tirelli, N., Cardullo, F., Habicher, T., Suter, U. W. & Diederich, F. Thermotropic behaviour of covalent fullerene adducts displaying 4-cyano-4'-oxybiphenyl mesogens. J. Chem. Soc. Perkin Trans. 2, 193–198 (2000)

    Article  Google Scholar 

  13. 13

    Felder, D., Heinrich, B., Guillon, D., Nicoud, J.-F. & Nierengarten, J.-F. A liquid crystalline supramolecular complex of C60 with a cyclotriveratrylene derivative. Chem. Eur. J. 6, 3501–3507 (2000)

    CAS  Article  Google Scholar 

  14. 14

    Dardel, B., Guillon, D., Heinrich, B. & Deschenaux, R. Fullerene-containing liquid-crystalline dendrimers. J. Mater. Chem. 11, 2814–2831 (2001)

    CAS  Article  Google Scholar 

  15. 15

    Chuard, T. & Deschenaux, R. Design, mesomorphic properties, and supramolecular organization of [60]fullerene-containing thermotropic liquid crystals. J. Mater. Chem. 12, 1944–1951 (2002)

    CAS  Article  Google Scholar 

  16. 16

    Suzuki, M., Furue, H. & Kobayashi, S. Polarizerless nanomaterial doped guest-host LCD exhibiting high luminance and good legibility. Mol. Cryst. Liq. Cryst. 368, 191–196 (2001)

    CAS  Article  Google Scholar 

  17. 17

    Kimura, M. et al. Self-organization of supramolecular complex composed of rigid dendritic porphyrin and fullerene. J. Am. Chem. Soc. 124, 5274–5275 (2002)

    CAS  Article  Google Scholar 

  18. 18

    Georgakilas, V. et al. Supramolecular self-asssembled fullerene nanostructures. Proc. Natl Acad. Sci. 99, 5075–5080 (2002)

    ADS  CAS  Article  Google Scholar 

  19. 19

    Sawamura, M., Iikura, H. & Nakamura, E. The first pentahaptofullerene metal complexes. J. Am. Chem. Soc. 118, 12850–12851 (1996)

    CAS  Article  Google Scholar 

  20. 20

    Tschierske, C. Non-conventional liquid crystals-the importance of micro-segregation for self-organization. J. Mater. Chem. 8, 1485–1508 (1998)

    CAS  Article  Google Scholar 

  21. 21

    Ruoff, R. S., Tse, D. S., Malhotra, R. & Lorents, D. C. Solubility of C60 in a variety of solvents. J. Phys. Chem. 97, 3379–3383 (1993)

    CAS  Article  Google Scholar 

  22. 22

    Iikura, H., Mori, S., Sawamura, M. & Nakamura, E. Endohedral homoconjugation in cyclopentadiene embedded in C60. Theoretical and electrochemical evidence. J. Org. Chem. 62, 7912–7913 (1997)

    CAS  Article  Google Scholar 

  23. 23

    Sawamura, M., Kuninobu, Y. & Nakamura, E. Half-sandwich metallocene embedded in a spherically extended π-conjugate system. Synthesis, structure, and electrochemistry of Rh(η5-C60Me5)(CO)2 . J. Am. Chem. Soc. 122, 12407–12408 (2000)

    CAS  Article  Google Scholar 

  24. 24

    Sawamura, M. et al. Hybrid of ferrocene and fullerene. J. Am. Chem. Soc. 124, 9354–9355 (2002)

    CAS  Article  Google Scholar 

  25. 25

    Manners, I. Putting metals into polymers. Science 294, 1664–1666 (2001)

    CAS  Article  Google Scholar 

Download references

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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