Molecular Surface Functionalization of Carbon Materials via Radical-Induced Grafting of Terminal Alkenes

Formation of functional monolayers on surfaces of carbon materials is inherently difficult because of the high bond strength of carbon and because common pathways such as S_N2 mechanisms cannot take place at surfaces of solid materials. Here, we show that the radical initiators can selectively abstract H atoms from H-terminated carbon surfaces, initiating regioselective grafting of terminal alkenes to surfaces of diamond, glassy carbon, and polymeric carbon dots. Nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) demonstrate formation of self-terminating organic monolayers linked via the terminal C atom of 1-alkenes. Density functional theory (DFT) calculations suggest that this selectivity is at least partially thermodynamic in origin, as significantly less energy is needed to abstract H atoms from carbon surfaces as compared to typical aliphatic compounds. The regioselectivity favoring binding to the terminal C atom of the reactant alkenes arises from steric hindrance encountered in bond formation at the adjacent carbon atom. Our results demonstrate that carbon surface radical chemistry yields a versatile, selective, and scalable approach to monolayer formation on H-terminated carbon surfaces and provide mechanistic insights into the surface selectivity and regioselectivity of molecular grafting.