Cage-Expansion of Fullerenes

Abstract

Despite the first proposal on the cage inflation of fullerenes in 1991, the chemical expansion of fullerenes has been still a formidable challenge. Herein, we provide an efficient methodology to expand [60] and [70]fullerene cages by the inclusion of totally C5N unit, giving nitrogen-containing closed structures as C₆₅N and C₇₅N with double fused heptagons. This method consists of two steps commenced with the construction of an opening by the reaction with triazine as a C3N source, followed by the cage reformation using <i>N</i>-phenylmaleimide as a C2 source. We also synthesized endohedral cages, demonstrating that the encapsulated H₂O molecule inside the C₇₅N cage prefers the orientation which maximizes the intramolecular interaction with the carbon wall. Additionally, we revealed the existence of a through-space magnetic dipolar interaction between the encapsulated H₂ molecule and the embedded N atom.