Superhalogens inside fullerenes X@C₂ (X = BO₂, BeF₃; 2n = 60, 70)

The exploration of endohedral fullerenes has garnered significant attention recently due to their distinctive chemical, electrochemical, and optoelectronic properties. Charge transfer, which usually occurs from encapsulated species to fullerenes, importantly affects the structures and properties of endohedral fullerenes. In this study, we theoretically investigated endohedral superhalogen fullerenes X@C₂ (X = BO₂, BeF₃; 2n = 60, 70), in which the charge is reversely transferred from the fullerene to the superhalogen, by using density functional theory calculations and ab initio molecular dynamics simulations. Both natural population analysis and the quantum theory of atoms in molecules confirm about one electron transfer from the fullerene to the superhalogen, resulting in the formal valence state of X^-@C₂⁺. Energy decomposition analysis on the interaction between the superhalogen and fullerene revealed that electrostatic energy contributes predominantly to the total interaction energy. These endohedral superhalogen fullerenes with cationic fullerenes were predicted to be able to serve as building blocks for one dimensional fullerene-based nanowires when combined with endohedral alkali-metallofullerenes with anionic fullerenes.