Hefei National Laboratory for Physical Sciences at Microscale, Key Laboratory of Materials for Energy Conversion, Chinese Academy of Sciences, Department of Materials Science and Engineering, Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China (USTC) , Hefei 230026, China.
State Key Laboratory of Materials Processing and Die & Mold Technology, College of Materials Science and Engineering, Huazhong University of Science and Technology (HUST) , Wuhan 430074, China.
J Am Chem Soc. 2016 Jan 13;138(1):207-14. doi: 10.1021/jacs.5b10115. Epub 2015 Dec 22.
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(x)Sc(3-x)N@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(x)Sc(3-x)N@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(x)Sc(3-x)N@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(x)Sc(3-x)N@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.
到目前为止，用于分离的内包金属富勒烯（EMFs）的金属主要限于稀土金属，而除了第 IVB 族金属之外，是否可以捕获其他 d 区过渡金属尚不清楚。本文报道了成功地将第 VB 族过渡金属钒（V）捕获到富勒烯笼中，得到了迄今未知的含 V 的 EMFs。分离出了两种新型含 V 的 EMFs--V(x)Sc(3-x)N@C80（x = 1,2）--并用 X 射线晶体学明确地确定了它们的分子结构，它们是由 I(h)(7)-C80 笼捕获的平面 VSc2N/V2ScN 簇组成。通过 UV-vis-NIR 和 ESR 光谱和电化学进一步表征了 V(x)Sc(3-x)N@I(h)(7)-C80（x = 1,2），结果表明 V(x)Sc(3-x)N@I(h)(7)-C80（x = 1,2）的电子和磁性性质可以通过改变捕获的 V 原子数（即 x 值）来调节。V(x)Sc(3-x)N@I(h)(7)-C80（x = 1,2）的分子结构和电子性质与基于镧系金属和相邻的第 IVB 族过渡金属 Ti 的报道的类似 EMFs 进行了比较，揭示了第 VB 族过渡金属 V 基 EMFs 的特殊性。
