Photochlorination of linear alkanes with 2-position selectivity using a metal-organic layer catalyst

Controlling regioselectivity in activating C–H bonds in linear alkanes is challenging, as their multiple secondary C–H bonds have quite similar dissociation energies, with no functional groups to differentiate between the bonds. Here, we coupled a ligand-to-metal charge transfer (LMCT)-based radical generation center and an amide functional group on a tailor-designed metal-organic layer (MOL) material. We achieved efficient photochlorination of linear alkanes with 2-position selectivity. For example, with n-hexane as the substrate, 2-chloro-n-hexane was obtained with 85% selectivity and a turnover number of 2,200 in 8 h, together with a high apparent quantum yield of ∼7% at room temperature. Mechanistic experiments suggested that the chlorine generation and installation of an amide group are important for the orchestration of the reactivity and the selectivity.