Theoretical Insight into the Ambiguous Endohedral Metallofullerene Er3C74: Covalent Interactions among Three Lanthanide Atoms

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• 作者：Yi-Jun Guo ; Hong Zheng ; Tao Yang ; Shigeru Nagase ; Xiang Zhao
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：August 17, 2015
• 年：2015
• 卷：54
• 期：16
• 页码：8066-8076
• 全文大小：638K
• ISSN：1520-510X

文摘

All of C₇₄-based endohedral metallofullerenes (EMFs) are found to be monometallofullerenes with the same D_3h(14246)-C₇₄ cage so far. An opening question is whether other C₇₄ cages could survive during the production of some novel C₇₄-EMFs. Theoretically, we studied the trimetallic endohedral fullerene Er₃C₇₄, the existence of which had been proven without any further characterizations. Two thermodynamically stable Er₃C₇₄ isomers were obtained, both of which could be expressed as Er₃@C₇₄, meaning that previously synthesized Er₃C₇₄ is indeed an endohedral trierbium fullerene. Besides the isomer with well-known D_3h(14246)-C₇₄ cage which obeys isolated pentagon rule (IPR), another one possesses the C₁(13771)-C₇₄ cage with two adjacent pentagons. Notably, it is the first time an endohedral metallofullerene containing the C₁(13771)-C₇₄ cage has been reported. Frontier orbitals analysis, bonding analysis in terms of quantum theory of atoms-in-molecule (QTAIM) and Mayer bond order, together with two-dimensional maps of electron localization function (ELF) and Laplacian of electron density of Er₃@D_3h(14246)-C₇₄ and Er₃@C₁(13771)-C₇₄ show obvious covalent interactions not only between metallic atoms and carbon cage but also among three erbium atoms. Finally, simulated IR spectra of Er₃@D_3h(14246)-C₇₄ and Er₃@C₁(13771)-C₇₄ were simulated, which should be useful to distinguish those two isomers.