Hu Shuaifeng, Zhao Pei, Shen Wangqiang, Ehara Masahiro, Xie Yunpeng, Akasaka Takeshi, Lu Xing
State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering , Huazhong University of Science and Technology , 1037 Luoyu Road , Wuhan 430074 , People's Republic of China.
Research Center for Computational Science , Institute for Molecular Science , Okazaki 444-8585 , Japan.
Inorg Chem. 2020 Feb 3;59(3):1940-1946. doi: 10.1021/acs.inorgchem.9b03269. Epub 2020 Jan 21.
Six dierbium carbide endohedral metallofullerenes have been synthesized and chromatographically isolated. Single-crystal X-ray diffractometry unambiguously ascertains their structures as ErC@(5)-C, ErC@(6)-C, ErC@(15)-C, ErC@(9)-C, ErC@(15)-C, and ErC@(32)-C, respectively. The Er···Er distances of the major erbium sites inside the (6)-C, (5)-C, (15)-C, (15)-C, (9)-C, and (32)-C cages are 3.801, 3.860, 4.062, 4.066, 4.307, and 4.372 Å, respectively, which show a linear tendency with an increase in the major axis of the fullerene cages (8.064, 8.238, 8.508, 8.582, 8.815, and 8.953 Å, respectively). Furthermore, the electrochemical and molecular orbital analyses reveal that the redox chemistry of the ErC@C isomers is associated with the carbon cage, which is different from the situations found for typical dimetallofullerenes, such as Y@C, Er@C, and Lu@C isomers, which show metal-dependent oxidation processes, indicating the importance of C insertion in carbide cluster metallofullerenes.
已合成并通过色谱法分离出六种碳化镱内嵌金属富勒烯。单晶X射线衍射法明确确定它们的结构分别为ErC@(5)-C、ErC@(6)-C、ErC@(15)-C、ErC@(9)-C、ErC@(15)-C和ErC@(32)-C。(6)-C、(5)-C、(15)-C、(15)-C、(9)-C和(32)-C笼内主要铒位点的Er···Er距离分别为3.801、3.860、4.062、4.066、4.307和4.372 Å，随着富勒烯笼长轴的增加（分别为8.064、8.238、8.508、8.582、8.815和8.953 Å）呈现出线性趋势。此外，电化学和分子轨道分析表明，ErC@C异构体的氧化还原化学与碳笼相关，这与典型的二金属富勒烯（如Y@C、Er@C和Lu@C异构体）的情况不同，后者显示出依赖金属的氧化过程，这表明碳插入在碳化物簇金属富勒烯中的重要性。
