Synthesis, isolation, and X-ray structural characterization of trifluoromethylated C90 fullerenes: C90(30)(CF3)18 and C90(35)(CF3)14
Abstract
Two CF3 derivatives of C90, C90(30)(CF3)18 and C90(35)(CF3)14, have been isolated via HPLC from the products of a high-temperature trifluoromethylation of a C76–C96 fullerene mixture with CF3I. Their molecular structures were determined by single crystal X-ray crystallography using synchrotron radiation. The addition patterns of the new compounds are discussed in comparison with those of the corresponding chlorinated C90.
Supporting agencies: This work was supported in part by the Russian Foundation for Basic Research (grants 12-03-00324 and 13-03-91332).
About the Authors
N. B. Tamm
Moscow State University
Russian Federation
Russian Federation
Department of Chemistry
Moscow
S. I. Troyanov
Moscow State University
Russian Federation
Russian Federation
Department of Chemistry
Moscow
References
1. P.W. Fowler, D.E. Manolopoulos. An Atlas of Fullerenes, Clarendon, Oxford, 392 p. (1995).
2. T.J.S. Dennis, T. Kai, K. Asato, T. Tomiyama, H. Shinohara, T. Yoshida, Y. Kobayashi, H. Ishiwatari, Y. Miyake, K. Kikuchi, Y. Achiba. Isolation and characterization by 13C NMR spectroscopy of [84]fullerene minor isomers. J. Phys. Chem. A, 103, P. 8747–8752 (1999).
3. Y. Miyake, T. Minami, K. Kikuchi, M. Kainosho, Y. Achiba. Trends in structure and growth of higher fullerenes isomer structure of C86 and C88. Mol. Cryst. Liq. Cryst., 340, P. 553–558 (2000).
4. N.B. Shustova, B.N. Newell, S.M. Miller, O.P. Anderson, R.D. Bolskar, K. Seppelt, A.A. Popov, O.V. Boltalina, S.H. Strauss. Discovering and verifying elusive fullerene cage isomers: structures of C2-p11-(C74-D3h)(CF3)12 and C2-p11-(C78-D3h(5))(CF3)12. Angew. Chem. Int. Ed., 46, P. 4111–4114 (2007).
5. K.S. Simeonov, K.Yu. Amsharov, M. Jansen. Connectivity of the chiral D2-symmetric isomer of C76 through a crystal structure determination of C76Cl18·TiCl4. Angew. Chem. Int. Ed., 46, P. 8419–8421 (2007).
6. E. Kemnitz, S.I. Troyanov. Chlorides of isomeric C78 fullerenes: C78(1)Cl30, C78(2)Cl30, and C78(2)Cl18. Mendeleev Commun., 20, P. 74–76 (2010).
7. K.S. Simeonov, K.Yu. Amsharov, M. Jansen. C80Cl12 — a chlorinated derivative of the chiral D2−C80 isomer: empirical rationale of halogen atoms addition pattern. Chem.–Eur. J., 15, P. 1812–1815 (2009).
8. S.I. Troyanov, N.B. Tamm. Crystal and molecular structures of trifluoromethyl derivatives of C82 fullerene: C82(CF3)12 and C82(CF3)18. Crystallogr. Rep., 55, P. 432–435 (2010).
9. N.B. Tamm, L.N. Sidorov, E. Kemnitz, S.I. Troyanov. Isolation and structural X-ray investigation of perfluoroalkyl derivatives of six cage isomers of C84. Chem.–Eur. J., 15, P. 10486-10492 (2009).
10. S.I. Troyanov, N.B. Tamm. Crystal and molecular structures of trifluoromethyl derivatives of fullerene C86, C86(CF3)16 and C86(CF3)18. Crystallogr. Rep., 54, P. 598–602 (2009).
11. S.I. Troyanov, N.B. Tamm. Cage connectivities of C88 (33) and C92 (82) fullerenes captured as trifluoromethyl derivatives, C88(CF3)18 and C92(CF3)16. Chem. Commun., P. 6035–6037 (2009).
12. S. Yang, T. Wei, E. Kemnitz, S.I. Troyanov. Four isomers of C96 fullerene structurally proven as C96Cl22 and C96Cl24. Angew. Chem. Int. Ed., 51, P. 8239–8242 (2012).
13. M. Yoshida, J. Aihara. Validity of the weighted HOMO–LUMO energy separation as an index of kinetic stability for fullerenes with up to 120 carbon atoms. Phys. Chem. Chem. Phys., 1, P. 227–230 (1999).
14. Y. Achiba, K. Kikuchi, Y. Aihara, T. Wakabayashi, Y. Miyake, M. Kainosho. Higher Fullerenes: Structure and Properties. Proceedings of “Science and Technology of Fullerene Materials” MRS Symposia, Pittsburgh, P. Bernier, et al. (Eds.), 359, P. 3–9 (1995).
15. Y. Achiba, K. Kikuchi, Y. Aihara, T. Wakabayashi, Y. Miyake, M. Kainosho. Trends in Large Fullerenes: Are They Balls or Tubes. The Chemical Physics of Fullerenes 10 (and 5) Years Later. Proceedings of the NATO Advanced Research Workshop, Varenna, Italy, June 12-16, 1995. Andreoni, W., Ed., Kluwer Academic Publishers: Dordrecht, Netherlands, P. 139–147 (1996).
16. G. Sun. Theoretical 13C NMR chemical shifts of the stable isomers of fullerene C90. Chem. Phys., 289, P. 371–380 (2003).
17. H. Yang, C.M. Beavers, Z. Wang, A. Jiang, Z. Liu, H. Jin, B.Q. Mercado, M.M. Olmstead, A.L. Balch. Isolation of a small carbon nanotube: the surprising appearance of D5h(1)−C90. Angew. Chem. Int. Ed., 49, P. 886–890 (2010).
18. H. Yang, B.Q. Mercado, H. Jin, Z. Wang, A. Jiang, Z. Liu, C.M. Beavers, M.M. Olmstead, A.L. Balch. Isolation and crystallographic identification of four isomers of Sm@C90. Chem. Commun., 47, P. 2068– 2070 (2011).
19. I.E. Kareev, A.A. Popov, I.V. Kuvychko, N.B. Shustova, S.F. Lebedkin, V.P. Bubnov, O.P. Anderson, K. Seppelt, S.H. Strauss, O.V. Boltalina. Synthesis and X-ray or NMR/DFT structure elucidation of twenty-one new trifluoromethyl derivatives of soluble cage isomers of C76, C78, C84, and C90. J. Am. Chem. Soc., 130, P. 13471–13489 (2008).
20. E. Kemnitz, S.I. Troyanov. Connectivity patterns of two C90 isomers provided by the structure elucidation of C90Cl32. Angew. Chem. Int. Ed., 48, P. 2584–2587 (2009).
21. S.I. Troyanov, S. Yang, C. Chen, E. Kemnitz. Six IPR isomers of C90 fullerene captured as chlorides: Carbon cage connectivities and chlorination patterns. Chem.–Eur. J., 17, P. 10622–10669 (2011).
22. www.mercorp.com
23. K. Chang, M.A. Fritz, N.B. Tamm, A.A. Goryunkov, L.N. Sidorov, C. Chen, S. Yang, E. Kemnitz, S.I. Troyanov. Synthesis, structure, and theoretical study of trifluoromethyl derivatives of C84(22) fullerene. Chem.–Eur. J., 19, P. 578-587 (2013).
24. D.V. Ignat’eva, A.A. Goryunkov, N.B. Tamm, I.N. Ioffe, L.N. Sidorov, S.I. Troyanov. Isolation and structural characterization of the most highly trifluoromethylated C70 fullerenes: C70(CF3)18 and C70(CF3)20. New J. Chem., 37, P. 299-302 (2013).
25. M.A. Lanskikh, K. Chang, N.B. Tamm, E. Kemnitz, S.I. Troyanov. Trifluoromethyl derivatives of C88(33) fullerene. Mendeleev Commun., 22, P. 136–137 (2012).
26. N.B. Tamm, L.N. Sidorov, E. Kemnitz, S.I. Troyanov. Crystal structures of C94(CF3)20 and C96(C2F5)12 reveal the cage connectivities in C94 (61) and C96 (145) fullerenes. Angew. Chem. Int. Ed., 48, P. 9102– 9104 (2009).
27. H. Liang, Y.-Z. Tan, T. Zhou, Z.-L. Chen, S.-Y. Xie, R.-B. Huang, L.-S. Zheng. C76Cl34: High chlorination of the inherent chiral fullerene with a helical configuration. Inorg. Chem., 49, P. 3089–3091 (2010).
28. I.N. Ioffe, O.N. Mazaleva, C. Chen, S.-F. Yang, E. Kemnitz, S.I. Troyanov. C76 fullerene chlorides and cage transformations. Structural and theoretical study. Dalton Trans., 40, P. 11005–11011 (2011).
29. S.M. Avdoshenko, A.A. Goryunkov, I.N. Ioffe, D.V. Ignat‘eva, L.N. Sidorov, P. Pattison, E. Kemnitz, S.I. Troyanov. Preparation, crystallographic characterization and theoretical study of C70(CF3)16 and C70(CF3)18. Chem. Commun., P. 2463–2465 (2006).
30. S.I. Troyanov, A.A. Popov. A [70]fullerene chloride, C70Cl16, obtained by the attempted bromination of C70 in TiCl4. Angew. Chem. Int. Ed., 44, P. 4215–4218 (2005).
31. N.B. Tamm, S.I. Troyanov. Trifluoromethyl derivatives of fullerene C76, C76(CF3)14−18. Mendeleev Commun., 20, P. 229–230 (2010).
32. Z. Slanina, X. Zhao, S.-L. Lee, E. Osawa. Computations on the IPR isomers of C ˜ 88 and C90. Scr. Mater. 43, P. 733–741 (2000).
33. M. Watanabe, D. Ishimaru, N. Mizorogi, M. Kiuchi, J. Aihara. Thermodynamically and kinetically stable isomers of the C88 and C90 fullerenes. J. Mol. Struct., - THEOCHEM, 726, P. 11–16 (2005).
Review
For citations:
Tamm N.B., Troyanov S.I. Synthesis, isolation, and X-ray structural characterization of trifluoromethylated C90 fullerenes: C90(30)(CF3)18 and C90(35)(CF3)14. Nanosystems: Physics, Chemistry, Mathematics. 2014;5(1):39-45.
Views:
4
Email this article 