Blue-Light-Driven Aerobic Oxidation via Superoxide Radical-Generating Zinc(II)-Organic Framework Photocatalyst

Abstract

The development of sustainable and efficient photocatalytic systems for aerobic oxidation is a crucial challenge in the field of green chemistry. In this study, we present the rational design and synthesis of a novel zinc(II)-organic framework (Zn-1D) by incorporating anthracene-based photoactive ligands with zinc(II)-oxo clusters. Zn-1D demonstrates significant absorption in the blue-light region (<450 nm), effective charge separation, and the ability to generate superoxide radicals (O2 •-).Structural analysis confirms a crystalline 1D chained structure with hierarchical porosity. Mechanistic investigations reveal a synergistic effect between anthracene-mediated light absorption and zinc(II)-mediated redox reactions. Under blue-light irradiation, Zn-1D exhibits outstanding catalytic performance in aerobic oxidation reactions, such as the thioether oxidation.The microporous channels of the framework stabilize reactive intermediates, preventing overoxidation. Moreover, its excellent chemical and thermal stability allow for five consecutive recycling cycles without loss of activity. This work provides a new model for noble-metal-free photocatalysis by utilizing MOF-confined dual-function sites for blue-light-driven organic transformations, thus promoting the development of sustainable synthetic methods.