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

doi:10.1021/ja109462j

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

67 Citations (Scopus)

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 E_1/2 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 language	English
Pages (from-to)	2672-2690
Number of pages	19
Journal	Journal of the American Chemical Society
Volume	133
Issue number	8
DOIs	https://doi.org/10.1021/ja109462j
Publication status	Published - 2011 Mar 2

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja109462j

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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

@article{ab79f3b28d554bd29e44db619b94a1e2,

title = "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",

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.",

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

year = "2011",

month = mar,

day = "2",

doi = "10.1021/ja109462j",

language = "English",

volume = "133",

pages = "2672--2690",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "8",

}

Shustova, NB, Peryshkov, DV, Kuvychko, IV, Chen, YS, MacKey, MA, Coumbe, CE, Heaps, DT, Confait, BS, Heine, T, Phillips, JP, Stevenson, S, Dunsch, L, Popov, AA, Strauss, SH & Boltalina, OV 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, vol. 133, no. 8, pp. 2672-2690. https://doi.org/10.1021/ja109462j

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. / Shustova, Natalia B.; Peryshkov, Dmitry V.; Kuvychko, Igor V. et al.
In: Journal of the American Chemical Society, Vol. 133, No. 8, 02.03.2011, p. 2672-2690.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Poly(perfluoroalkylation) of metallic nitride fullerenes reveals addition-pattern guidelines

T2 - Synthesis and characterization of a family of Sc3N@C80(CF3)n (n = 2-16) and their radical anions

AU - Shustova, Natalia B.

AU - Peryshkov, Dmitry V.

AU - Kuvychko, Igor V.

AU - Chen, Yu Sheng

AU - MacKey, Mary A.

AU - Coumbe, Curtis E.

AU - Heaps, David T.

AU - Confait, Bridget S.

AU - Heine, Thomas

AU - Phillips, J. Paige

AU - Stevenson, Steven

AU - Dunsch, Lothar

AU - Popov, Alexey A.

AU - Strauss, Steven H.

AU - Boltalina, Olga V.

PY - 2011/3/2

Y1 - 2011/3/2

N2 - 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.

AB - 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.

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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

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