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

2 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.