Photosensitizing Metal–Organic Framework Enabling Visible-Light-Driven Proton Reduction by a Wells–Dawson-Type Polyoxometalate

A simple and effective charge-assisted self-assembly process was developed to encapsulate a noble-metal-free polyoxometalate (POM) inside a porous and phosphorescent metal-organic framework (MOF) built from [Ru(bpy)3](2+)-derived dicarboxylate ligands and Zr6(μ3-O)4(μ3-OH)4 secondary building units. Hierarchical organization of photosensitizing and catalytic proton reduction components in such a POM@MOF assembly enables fast multielectron injection from the photoactive framework to the encapsulated redox-active POMs upon photoexcitation, leading to efficient visible-light-driven hydrogen production. Such a modular and tunable synthetic strategy should be applicable to the design of other multifunctional MOF materials with potential in many applications.