Electrostatic Confinement of Photosensitizers within Molybdenum-Sulfur Cluster-Based Supramolecular Matrices for Efficient Dual-Photocatalysis: Hydrogen Evolution and Trifluoromethylation.

Enhancing charge transfer efficiency between molecular photosensitizers and catalytic units remains a pivotal yet challenging objective in developing advanced photocatalytic systems. Herein, we present a crystallographic self-assembly strategy to construct Ru@MoS-MBIZ─a periodically ordered supramolecular architecture, wherein cationic photosensitizers, [Ru(bpy)3]2+, are electrostatically immobilized within cavities formed by anionic molybdenum-sulfur (Mo-S) clusters ([Mo3S7(MBIZ)3]-), enabling spatially defined coupling between light-harvesting and catalytic moieties. The atomically precise arrangement not only enhances structural stability and light absorption but also optimizes the electronic structure and energy-level alignment, facilitating efficient charge separation and directional charge transfer. The integrated system exhibits outstanding photocatalytic performance for hydrogen production with an impressive generation rate of 46 mmol g-1 h-1─118 and 4.5 times higher than those of pristine MoS-MBIZ and a physical mixture of [Ru(bpy)3]Cl2/MoS-MBIZ, respectively, surpassing most noble-metal-assisted crystalline photocatalysts. Notably, this integrated strategy enables a leap from single- to dual-function photocatalysis, concurrently achieving visible-light-driven trifluoromethylation with >85% yield for trifluorotoluene and a broad substrate scope covering 25 diverse (hetero)arenes and pharmaceuticals, marking the first extension of Mo-S clusters to organic photosynthesis. Mechanistic investigations through experimental and theoretical analyses confirm enhanced charge separation and directional electron transfer from Ru to Mo centers. This work establishes a blueprint for programmable multifunctional photocatalysts via electrostatic confinement and crystallographic integration.