Reactivity of the superhalogen/superalkali ion encapsulated C60 fullerenes

Abstract

The Diels-Alder cycloaddition reaction between 1,3-cyclohexadiene and a series of C60 fullerenes with encapsulated (super)alkali/(super)halogen species (Li+@C60, Li2F+@C60, Cl-@C60, and LiF2-@C60) was explored by means of DFT calculations. Reactivity of the ion encapsulated systems was compared to the parental C60 fullerene. Significant enhancement in reactivity was found for cation encapsulated Li+/Li2F+@C60 complexes. The cycloadduct formed by LiF2-@C60 was found to be the most thermodynamically favorable among the studied ones. In contrast, encapsulation of Cl- anion leads to the disfavor of cycloaddition reaction both kinetically and thermodynamically. Higher activation energy barrier and less stability of the reaction product in the case of Cl-@C60 were associated with higher deformation energies of fullerene cage and smaller interaction energy between the reactants in comparison to the other studied complexes