Department of Engineering Science, The University of Electro-Communications, Chofu 182-8585, Japan.
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan.
Molecules. 2017 Jul 14;22(7):1179. doi: 10.3390/molecules22071179.
Exohedral derivatization of endohedral metallofullerenes (EMFs) has been exploited as a useful method for characterizing the structural and chemical properties of EMFs, and for functionalizing them for potential applications. The introduction of heteroatoms, such as electropositive silicon atoms, to fullerene cages is a novel functionalization method that remarkably affects the electronic characteristics of fullerenes. This review comprehensively describes the results of the reactions of monometallofullerene, dimetallofullerene, and trimetallic nitride template EMFs with disilirane, silirane, silylene, and digermirane, which afforded the corresponding silylated and germylated fullerenes. Several examples emphasize that exohedral functionalization regulates the dynamic behaviors of the encapsulated metal atoms and clusters in the fullerene cages. The electronic effects of silyl and germyl groups are represented by comparing the redox properties of silylated and germylated EMFs with those of other EMFs derivatized with carbon-atom-based functional groups.
金属富勒烯（EMFs）的外壳衍生已被用作一种有用的方法来表征 EMFs 的结构和化学性质，并对其进行功能化，以用于潜在的应用。将杂原子（如正电性的硅原子）引入富勒烯笼中是一种新颖的功能化方法，可显著影响富勒烯的电子特性。本综述全面描述了单金属富勒烯、双金属富勒烯和三金属氮化物模板 EMFs 与二硅烷、硅烷、硅烯和二锗烷的反应结果，得到了相应的硅烷化和锗烷化富勒烯。有几个例子强调了外壳官能化调节了金属原子和团簇在富勒烯笼内的动态行为。通过比较硅烷化和锗烷化 EMFs 与用基于碳原子的官能团衍生的其他 EMFs 的氧化还原性质，来表示硅烷基和锗烷基的电子效应。
