Poly(perfluoroalkylation) of Metallic Nitride Fullerenes Reveals Addition-Pattern Guidelines: Synthesis and Characterization of a Family of Sc3N@C80(CF3)n<

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• 作者：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
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：March 2, 2011
• 年：2011
• 卷：133
• 期：8
• 页码：2672-2690
• 全文大小：1562K
• 年卷期：v.133,no.8(March 2, 2011)
• ISSN：1520-5126

文摘

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鈭抳is/NIR, ESR), structural and electrochemical methods. For two new compounds, Sc₃N@C₈₀(CF₃)₁₀ and Sc₃N@C₈₀(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 Sc₃N@C₈₀(CF₃)_n (n = 2-16). Electrochemical studies revealed that Sc₃N@C₈₀(CF₃)_n derivatives are easier to reduce than Sc₃N@C₈₀, the shift of E_1/2 potentials ranging from +0.11 V (n = 2) to +0.42 V (n = 10). Stable radical anions of Sc₃N@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@C₈₀ making them attractive versatile platforms for the design of molecular and supramolecular materials of fundamental and practical importance.