Selective Photooxidation of Amines and Sulfides Triggered by a Superoxide Radical Using a Novel Visible-Light-Responsive Metal-Organic Framework.

Photocatalysis is an efficient and sustainable approach to convert solar energy into chemical energy, simultaneously supplying valuable chemicals. In this study, a novel metal-organic framework (MOF) compound is constructed from anthracene-based organic linkers, which shows visible-light absorption and efficient photoinduced charge generation property. It was applied for triggering photooxidation of benzylamines and sulfides in the presence of environmental benign oxidants of molecular oxygen or hydrogen peroxide. Results show that it is a highly selective photocatalyst for oxidation reactions to produce valuable imines or sulfoxides. We further investigate the underlying mechanism for these photocatalytic reactions by recognizing reactive oxygen species in the reactions. It has been demonstrated that the superoxide radical (O), generated by electron transfer from a photoexcited MOF to oxidants, serves as the main active species for the oxidations. The work demonstrates the great potential of photoactive MOFs for the transformation of organic chemicals into valuable complexes.