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

Abstract

All of C74-based endohedral metallofullerenes (EMFs) are found to be monometallofullerenes with the same D3h(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 D3h(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@D3h(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@D3h(14246)-C74 and Er3@C1(13771)-C74 were simulated, which should be useful to distinguish those two isomers.