Repurposing of oxazolone chemistry: gaining access to functionalized graphene nanosheets in a top-down approach from graphite†
Solvent-free 1,3-dipolar cycloaddition (1,3-DC) reactions between graphite flakes and mesoionic oxazolones were carried out by heating the resulting solid mixture at mild temperatures (70–120 °C). The direct functionalization and delamination of graphite flakes into few layers of graphene nanosheets was confirmed by micro-Raman and X-ray photoelectron spectroscopies, scanning transmission electron microscopy and thermogravimetric analysis. The 1,3-DC reactions of mesoionic dipoles have been investigated with density functional theory to model graphene, exploring three different pathways: center, corner and edge. These theoretical calculations highlighted that the 1,3-DC reaction can proceed both through a concerted mechanism competing with a stepwise one involving a zwitterionic intermediate. The irreversible decarboxylation inherent in the last step justifies the high degree of functionalization experimentally observed, representing the driving force of the process.