Chemical reactivity inside carbon cages: theoretical insights from a fullerene confinement

Abstract

In this paper, we investigate two model reactions (an electrocyclic ring closure and a tautomerism equilibrium) in different sized fullerene cages to explore the intricate details of the confinement effect in chemistry and in chemical reactivity. Fullerene cages offers, with their unique geometry and electronic properties, an ideal theoretical model to explore confinement-induced alterations in reaction pathways and energy barriers. Computational results demonstrate that the induced confinement may significantly influence the thermodynamics and kinetics of the chemical processes under study through a comparative investigation of reactions in various fullerene cage sizes and their occurrence in gas phase. This theoretical investigation intends to improve our knowledge of molecular confinement events, while also highlighting the potential use of fullerene cages as adjustable nanoreactors for regulating and improving chemical reactivity.