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

Authors

Natalia B. Shustova, Colorado State University
Dmitry V. Peryshkov, Colorado State University
Igor V. Kuvychko, Colorado State University
Yu-Sheng Chen, University of ChicagoFollow
Mary A. Mackey, University of Southern Mississippi
Curtis E. Coumbe, University of Southern Mississippi
David T. Heaps, University of Southern Mississippi
Bridget S. Confait, University of Southern Mississippi
Thomas Heine, Jacobs University
J. Paige Phillips, University of Southern MississippiFollow
Steven Stevenson, University of Southern Mississippi
Lothar Dunsch, Leibniz Institute for Solid State and Materials Research
Alexey A. Popov, Leibniz Institute for Solid State and Materials Research
Steven H. Strauss, Colorado State University
Olga V. Boltalina, Colorado State University

Document Type

Article

Publication Date

3-1-2011

Department

Chemistry and Biochemistry

School

Mathematics and Natural Sciences

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@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.

Publication Title

Journal of the American Chemical Society

Volume

133

Issue

8

First Page

2672

Last Page

2690

Recommended Citation

Shustova, N. B., Peryshkov, D. V., Kuvychko, I. V., Chen, Y., Mackey, M., Coumbe, C., Heaps, D., Confait, B., 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.
Available at: https://aquila.usm.edu/fac_pubs/8885