Synthesis and metal-binding properties of [60]fullerene-linked calix[4]arenes: an approach to ‘exohedral metallofullerenes’

Abstract

‘Fullerenocalixarenes’ in which [60]fullerene is covalently linked through two ionophoric chains to a cone-calix[4]arene 1 or to a 1,3-alternate calix[4]arene 2 have been synthesized for the first time: although the absorption spectrum of 2 is scarcely changed upon addition of metal cations, that of 1 is affected by added Li⁺, Na⁺ and Ag⁺, indicating the formation of exohedral [60]fullerene–metal complexes.

References

1. D. S. Bethune, R. D. Johnson, J. R. Salem, M. S. de Vries and C. S. Yonnori, Nature, 1993, 123, 366.
2. A. Gügel, A. Kraus, J. Spickermann, P. Belik and K. Müllen, Angew. Chem., Int. Ed. Engl., 1994, 33, 559; A. Kraus, A. Gügel, P. Belik, M. Walter and K. Müllen, Tetrahedron, 1995, 51, 9927.
3. S. N. Davey, D. A. Leigh, A. E. Moody, L. W. Tetler and F. A. Wade, J. Chem. Soc., Chem. Commun., 1994, 397.
4. J. Osterodt, M. Nieger, P.-M. Windscheif and F. Vögtle, Chem. Ber., 1993, 126, 2331; J. Osterodt, A. Zett and F. Vögtle, Tetrahedron, 1996, 52, 4949.
5. F. Diederich, U. Jonas, V. Gramilich, A. Herrmann, H. Ringsdorf and C. Thilgen, Helv. Chim. Acta, 1993, 76, 2445; U. Jonas, F. Cardullo, P. Belik, F. Diederich, A. Gügel, E. Harth, A. Herrmann, L. Isaacs, K. Müllen, H. Ringsdorf, C. Thilgen, P. Uhlmann, A. Vasella, C. A. A. Waldraff and M. Walter, Chem. Eur. J., 1995, 1, 243.
6. A. Ikeda and S. Shinkai, Chem. Lett., 1996, 803.
7. A. Ikeda, C. Fukuhara and S. Shinkai, Tetrahedron Lett., 1996, 37, 7091.
8. A. Ikeda, C. Fukuhara and S. Shinkai, Chem. Lett., 1997, 407.
9. J. L. Atwood, G. A. Koutsantonis and C. L. Raston, Nature, 1994, 368, 229.
10. C. L. Raston, J. L. Atwood, P. J. Nichols and I. B. N. Sudria, Chem. Commun., 1996, 2615.
11. T. Suzuki, K. Nakashima and S. Shinkai, Chem. Lett., 1994, 699.
12. T. Suzuki, K. Nakashima and S. Shinkai, Tetrahedron Lett., 1995, 36, 249.
13. T. Haino, M. Yanase and Y. Fukazawa, Angew. Chem., Int. Ed. Engl., 1997, 36, 360.
14. K. Araki, K. Akao, A. Ikeda, T. Suzuki and S. Shinkai, Tetrahedron Lett., 1996, 37, 73.
15. A. Ikeda, M. Yoshimura and S. Shinkai, Tetrahedron Lett., 1997, 38, 2107.
16. For comprehensive reviews see C. D. Gutsche, Calixarenes, Royal Society of Chemistry, Cambridge, 1989; Calixarenes, eds. J. Vicens and V. Böhmer, Kluwer Academic Express, Dordrecht, 1991; V. Böhmer, Angew. Chem., Int. Ed. Engl., 1995, 34, 713; S. Shinkai, Tetrahedron, 1993, 49, 8933; H. Otsuka and S. Shinkai, Supramol. Sci., 1996, 3, 189.
17. F. Ohseto and S. Shinkai, Chem. Lett., 1993, 2045.
18. A. Ikeda, T. Tsudera and S. Shinkai, J. Org. Chem., 1997, 62, 3568.
19. T. Grösser, M. Prato, V. Lucchini, A. Hirsch and F. Wudl, Angew. Chem., Int. Ed. Engl., 1995, 34, 1343.
20. A. Ikeda and S. Shinkai, Tetrahedron Lett., 1992, 33, 7385.
21. A. Ikeda and S. Shinkai, J. Am. Chem. Soc., 1994, 116, 3102 and references cited therein.
22. A. Ikeda, H. Tsuzuki and S. Shinkai, J. Chem. Soc., Perkin Trans. 2, 1994, 2073.
23. F. Vögtle, J. Gross, C. Seel and M. Nieger, Angew. Chem., Int. Ed. Engl., 1992, 31, 1069 and references cited therein.
24. For the π-donor participation see: M. Iyoda, Y. Kuwatani, T. Yamauchi and J. Oda, J. Chem. Soc., Chem. Commun., 1988, 65; R. Leookes and F. Vögtle, Chem. Ber., 1983, 116, 215; J.-L. Pierre, P. Baret, P. Chautemps and M. Armand, J. Am. Chem. Soc., 1981, 103, 2986; H. C. Kang, A. W. Hanson, B. Eaton and V. Boekelheide, J. Am. Chem. Soc., 1985, 107, 1079; F. R. Heirtzler, H. Hopf, P. G. Jones, P. Bubenitschek and V. Lehne, J. Org. Chem., 1993, 58, 2781; J. E. Gano, G. Subramaniam and R. Birnbaum, J. Org. Chem., 1990, 55, 4760.
25. For a theoretical consideration of the cation-π interaction see D. A. Dougherty, Science, 1996, 271, 163.
26. A. Casnati, P. Minari, A. Pochini, R. Ungaro, W. F. Nigenhuis, F. de Jong and D. N. Reinhoudt, Isr. J. Chem., 1992, 32, 79.
27. F. Inokuchi, Y. Shiomi, H. Kawabata, T. Sakaki and S. Shinkai, Chem. Lett., 1993, 1595.
28. A. V. Hill, J. Physiol., 1910, 40, iv–vii.
29. H. A. Benesi and J. H. Hildebrand, J. Am. Chem. Soc., 1949, 71, 2073.