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

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• 作者：Tao Wei ; Song Wang ; Xing Lu ; Yuanzhi Tan ; Jing Huang ; Fupin Liu ; Qunxiang Li ; Suyuan Xie ; Shangfeng Yang
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：January 13, 2016
• 年：2016
• 卷：138
• 期：1
• 页码：207-214
• 全文大小：406K
• ISSN：1520-5126

文摘

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—V_xSc_3–xN@C₈₀ (x = 1, 2)—were isolated, and their molecular structures were unambiguously determined by X-ray crystallography to be I_h(7)-C₈₀ cage entrapping the planar VSc₂N/V₂ScN clusters. V_xSc_3–xN@I_h(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 V_xSc_3–xN@I_h(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 V_xSc_3–xN@I_h(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.