Entrapping a Group-VB Transition Metal, Vanadium, within an Endohedral Metallofullerene: VxSc3–xN@Ih-C80 (x = 1, 2)

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Abstract
So far the entrapped metals for the isolated endohedral metallofullerenes (EMFs) are primarily limited to rare earth metals, whereas except group-IVB metals, whether it is possible to entrap other d-block transition metals remains unclear. Herein we report the successful entrapment of the group-VB transition metal vanadium(V) into fullerene cage, affording the heretofore unknown V-containing EMFs. Two novel V-containing EMFs—VxSc3–xN@C80 (x = 1, 2)—were isolated, and their molecular structures were unambiguously determined by X-ray crystallography to be Ih(7)-C80 cage entrapping the planar VSc2N/V2ScN clusters. VxSc3–xN@Ih(7)-C80 (x = 1, 2) were further characterized by UV–vis–NIR and ESR spectroscopies and electrochemistry, revealing that the electronic and magnetic properties of VxSc3–xN@Ih(7)-C80 (x = 1, 2) are tunable upon varying the number of entrapped V atoms (i.e., x value). The molecular structures and electronic properties of VxSc3–xN@Ih(7)-C80 (x = 1, 2) were further compared with those of the reported analogous EMFs based on lanthanide metals and the adjacent group-IVB transition metal Ti, revealing the peculiarity of the group-VB transition metal V-based EMFs.
Funding Information
  • Ministry of Science and Technology of the People's Republic of China (2014CB921101)
  • National Natural Science Foundation of China (21132007, 21371164, 21473168)

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