Pivotal Role of Nonmetal Atoms in the Stabilities, Geometries, Electronic Structures, and Isoelectronic Chemistry of Sc3X@C80 (X = C, N, and O)

The thermodynamic and dynamic stabilities of Sc3X@C80 (X = C, N, and O) are explored via density functional theory combined with statistical thermodynamic analysis and ab initio molecular dynamics. It is the first time to comprehensively consider the effect of nonmetal atoms on trimetallic endohedral clusterfullerenes. Relative to Sc3X@Ih (31924)‐C80 (X = N and O) with general six‐electron transfer, an intriguing electronic structure of unexplored Sc3C@D5h (31923)‐C80 with thermodynamic and dynamic stabilities is clearly disclosed. Natural bond orbitals and charge decomposition analysis simultaneously suggest that one unpaired electron appears on the cage for neutral Sc3C@D5h (31923)‐C80, which could be prospectively stabilized by effective exohedral derivatization and ionization in the future. Moreover, isoelectronic endohedral clusterfullerenes, (Sc3C@C80)−, Sc3N@C80, and (Sc3O@C80)+, are also uniquely taken into account. The geometries, electronic structures, reactivities, and reactive sites of isoelectronic species are examined, and it turns out that all the three isoelectronic species would rather electrophilic than nucleophilic reactions. © 2019 Wiley Periodicals, Inc.