Covalent functionalization by using blue light activated radicals: on the reaction mechanisms of arylazo sulfone binding on graphene.

Covalent functionalization of graphene presents a pivotal strategy to enhance its surface properties and overcome inherent chemical inertness. While diazonium salts have been extensively utilized for this purpose, their limitations necessitate exploration of alternative approaches. Arylazo sulfones, such as diazonium salt derivatives serving as chromophores, offer a promising solution, enabling photochemical reactions under visible light. Here, we propose a novel method for rapid covalent photofunctionalization of chemical vapor deposition (CVD) graphene on copper substrates using arylazo sulfones. The generation of aryl radicals - chlorobenzene in this case - was achieved through blue light LED irradiation of 4-chlorophenylazo methyl sulfone solution in acetonitrile. Efficient surface covalent modification of graphene was verified by observing (i) the photogeneration of radicals with a decrease in the π-π* band absorbance and an increase in the n-π* of arylazosulfone solution by UV-Vis spectroscopy; (ii) an increase in C sp

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