Design of a Polyoxometalate-Based Metal–Organic Framework for Photocatalytic C(sp³)–H Oxidation of Toluene

A powerful and promising route for developing novel photocatalysts for light-driven toluene oxidation in water under mild conditions is presented. Herein, a novel polyoxometalate-based metal–organic framework (POMOF), {Co₄W₂₂-DPNDI}, is prepared by incorporating the unusual Co₄-sandwiched POM anion [Co₄(μ-OH)₂(SiW₁₁O₃₉)₂]^10– ({Co₄W₂₂}) and the photoactive organic bridging link N,N′-bis­(4-pyridylmethyl)­naphthalene diimide (DPNDI) into a framework. {Co₄W₂₂} is a good candidate for photocatalytic water oxidation. DPNDI is easily excited to form the radical species DPNDI* in the presence of an electron donor, which is beneficial for activation of the inert O₂. Anion···π interactions and covalent bonds between {Co₄W₂₂} and DPNDI facilitate electron–hole separation and electron transfer. {Co₄W₂₂-DPNDI} displays high catalytic activity for the activation of the C­(sp³)–H bond of toluene using light as a driving force and inexpensive water as an oxygen source under mild conditions. In particular, the yield and selectivity are improved by replacing oxygen with water, which may be ascribed to the release of protons during the water oxidation process that facilitate the generation of ^•OH.