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)perfluoroalkylated metallic nitride cluster fullerenes was prepared in high-temperature reactions and characterized by spectroscopic (MS, (19)F NMR, UV-vis/NIR, ESR), structural and electrochemical methods. For two new compounds, Sc(3)N@C(80)(CF(3))(10) and Sc(3)N@C(80)(CF(3))(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 ((19)F NMR spectroscopy and single crystal X-ray diffraction) studies and exhaustive quantum chemical calculations of the structures of Sc(3)N@C(80)(CF(3))(n) (n = 2-16). Electrochemical studies revealed that Sc(3)N@C(80)(CF(3))(n) derivatives are easier to reduce than Sc(3)N@C(80), 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(3)N@C(80)(CF(3))(n) were generated in solution and characterized by ESR spectroscopy, revealing their (45)Sc hyperfine structure. Facile further functionalizations via cycloadditions or radical additions were achieved for trifluoromethylated Sc(3)N@C(80) making them attractive versatile platforms for the design of molecular and supramolecular materials of fundamental and practical importance.
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
authors.forename: Natalia B
authors.initials: NB
authors.lastname: Shustova
authors.forename: Dmitry V
authors.initials: DV
authors.lastname: Peryshkov
authors.forename: Igor V
authors.initials: IV
authors.lastname: Kuvychko
authors.forename: Yu-Sheng
authors.initials: YS
authors.lastname: Chen
authors.forename: Mary A
authors.initials: MA
authors.lastname: Mackey
authors.forename: Curtis E
authors.initials: CE
authors.lastname: Coumbe
authors.forename: David T
authors.initials: DT
authors.lastname: Heaps
authors.forename: Bridget S
authors.initials: BS
authors.lastname: Confait
authors.forename: Thomas
authors.initials: T
authors.lastname: Heine
authors.forename: J Paige
authors.initials: JP
authors.lastname: Phillips
authors.forename: Steven
authors.initials: S
authors.lastname: Stevenson
authors.forename: Lothar
authors.initials: L
authors.lastname: Dunsch
authors.forename: Alexey A
authors.initials: AA
authors.lastname: Popov
authors.forename: Steven H
authors.initials: SH
authors.lastname: Strauss
authors.forename: Olga V
authors.initials: OV
authors.lastname: Boltalina
mesh_terms: D000478:Alkylation; D000838:Anions / Q000737:chemistry; D018360:Crystallography, X-Ray; D005466:Fluorocarbons / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D037741:Fullerenes / Q000737:chemistry*; D008958:Models, Molecular; D009570:Nitriles / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D012538:Scandium / Q000737:chemistry*
chemical_list: D000838:Anions; D005466:Fluorocarbons; D005609:Free Radicals; D037741:Fullerenes; D009570:Nitriles; D011108:Polymers; D012538:Scandium