Decatungstate-Based Metal–Organic Framework for Photocatalytic Aerobic Oxidation of Saturated C–H Bonds via Hydrogen Atom Transfer and Single-Electron Transfer

Abstract Photocatalytic oxidation of hydrocarbons to carboxyl or carbonyl derivatives is considered a highly promising method, yet finding highly active and stable photocatalysts remains challenging. Herein, a decatungstate-based metal–organic framework (POMOF) photocatalyst, CuW10–DPNDI, engineered for efficient photocatalytic C–H bond activation, was prepared by incorporating [W10O32]4– as the photoactive component for HAT and SET, copper metal ions, and the photosensitizer ligand N,N’-bis(4-pyridylmethyl)naphthalenediimide (DPNDI). CuW10–DPNDI exhibits high photocatalytic activity for the oxidation of inert C(sp3)–H bonds under mild white-light irradiation. The coordination bonds between copper(I), DPNDI, and [W10O32]4–, hydrogen bonds, along with π···π stacking interactions, collectively enhance photoinduced electron–hole separation and facilitate charge transfer among components. The mechanism of C–H bond activation is mediated by [W10O32]4– anions via a HAT pathway, where the synergistic contribution of photosensitizer DPNDI and copper(I) enhances visible-light absorption and narrows the band gap. This work not only provides a sustainable strategy for C–H bond oxidation but also establishes POMOFs as robust platforms for advanced photocatalytic organic transformations.