Metal-Dependent Stability of Pristine and Functionalized Unconventional Dimetallofullerene M2@Ih-C80
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- 作者：Zhiyong Wang ; Ryo Kitaura ; Hisanori Shinohara
- 刊名：Journal of Physical Chemistry C
- 出版年：2014
- 出版时间：June 26, 2014
- 年：2014
- 卷：118
- 期：25
- 页码：13953-13958
- 全文大小：339K
- ISSN：1932-7455
文摘
The unstable fullerene Ih-C80 can be stabilized greatly by encapsulation of two rare-earth metal atoms in its interior. Here we present a theoretical study on the electronic structures and stabilities of dimetallofullerene M2@Ih-C80 (M = Y, La, Gd, Lu). Density functional calculations demonstrate that La2@Ih-C80 has a closed-shell configuration, whereas Y2@Ih-C80 has a triplet ground state. Unlike La2@Ih-C80 with a high stability, Y2@Ih-C80 is found to be a highly reactive radical due to the unpaired electron distributed on the fullerene cage. Such characteristic properties of La2@Ih-C80 and Y2@Ih-C80 originate from the different energy levels of the metal-based molecular orbitals. Y2@Ih-C80 can be stabilized, however, through exterior functionalization with a CF3 group. Interestingly, metallofullerenes Gd2@Ih-C80 and Lu2@Ih-C80 have similar frontier molecular orbitals and chemical stabilities to those of Y2@Ih-C80.