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Published on: December 29, 2016
Ca@Pb12: A Viable All-Main-Group-Metal Endofullerene That Imitates the Transition Metals
Bin Huo1, Xiao-Ling Guan1, Caixia Yuan1
1Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Key Laboratory of Chemical Biology and Molecular Engineering of Ministry of Education, Institute of Molecular Science, Shanxi University, Taiyuan 030006, People's Republic of China.
Abstract:
Herein, we report the Ca@Pb12 cluster, an all-main-group-metal endofullerene possessing the highly symmetric icosahedral (I) Platonic solid structure. The endohedral environment endows the Ca atom with concrete transition-metal-like bonding behaviors, as evidenced by the 18e (in 3d104s24p6 configuration) valence shell structure and five strong Pb12 → Ca(3d) dative bonds, whose orbital interaction energy (ΔEorb, -134.2 kcal/mol) represents 54.9% of total ΔEorb (-244.4 kcal/mol) between Ca2+ and [Pb12]2-. Moreover, since the favorable orbital interactions can compensate for the enlarged steric repulsion during encapsulation, Ca@Pb12 is thermodynamically stable, dynamically rigid (up to 1300 K), and electronically robust, as verified by large HOMO-LUMO gaps (4.58 eV), high vertical detachment energy (6.39 eV), and low electron affinity (-0.71 eV). It is the first viable all-main-group-metal endofullerene, where the guest alkaline earth metal exhibits the typical bonding behaviors of transition metals.
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