Poly(perfluoroalkylation) of metallic nitride fullerenes reveals addition-pattern guidelines: Synthesis and characterization of a family of Sc3N@C80(CF3)n (n = 2-16) and their radical anions

Natalia B. Shustova, Dmitry V. Peryshkov, Igor V. Kuvychko, Yu Sheng Chen, Mary A. MacKey, Curtis E. Coumbe, David T. Heaps, Bridget S. Confait, Thomas Heine, J. Paige Phillips, Steven Stevenson, Lothar Dunsch, Alexey A. Popov, Steven H. Strauss, Olga V. Boltalina

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Abstract

A family of highly stable (poly)perfluoroalky-lated metallic nitride cluster fullerenes was prepared in high-temperature reactions and characterized by spectroscopic (MS, 19F NMR, UV-vis/NIR, ESR), structural and electrochemical methods. For two new compounds, Sc3N@C 80(CF3)10 and Sc3N@C 80(CF3)12, single crystal X-ray structures are determined. Addition pattern guidelines for endohedral fullerene derivatives with bulky functional groups are formulated as a result of experimental ( 19F NMR spectroscopy and single crystal X-ray diffraction) studies and exhaustive quantum chemical calculations of the structures of Sc 3N@C80(CF3)n (n = 2-16). Electrochemical studies revealed that Sc3N@C80(CF 3)n derivatives are easier to reduce than Sc 3N@C80, the shift of E1/2 potentials ranging from +0.11 V (n = 2) to +0.42 V (n = 10). Stable radical anions of Sc 3N@C80(CF3)n were generated in solution and characterized by ESR spectroscopy, revealing their 45Sc hyperfine structure. Facile further functionalizations via cycloadditions or radical additions were achieved for trifluoromethylated Sc3N@C 80 making them attractive versatile platforms for the design of molecular and supramolecular materials of fundamental and practical importance.

Original languageEnglish
Pages (from-to)2672-2690
Number of pages19
JournalJournal of the American Chemical Society
Volume133
Issue number8
DOIs
Publication statusPublished - 2011 Mar 2

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Shustova, N. B., Peryshkov, D. V., Kuvychko, I. V., Chen, Y. S., MacKey, M. A., Coumbe, C. E., Heaps, D. T., Confait, B. S., Heine, T., Phillips, J. P., Stevenson, S., Dunsch, L., Popov, A. A., Strauss, S. H., & Boltalina, O. V. (2011). Poly(perfluoroalkylation) of metallic nitride fullerenes reveals addition-pattern guidelines: Synthesis and characterization of a family of Sc3N@C80(CF3)n (n = 2-16) and their radical anions. Journal of the American Chemical Society, 133(8), 2672-2690. https://doi.org/10.1021/ja109462j