A Green Environmental Protection Photocatalytic Molecular Reactor for Aerobic Oxidation of Sulfide to Sulfoxide

Abstract The design and synthesis of metal‐organic frameworks (MOFs) as photocatalytic molecular reactors for varied reactions have drawn great attention. In this work, we designed a novel photoactive perylenediimides‐based (PDI) carboxylate ligand N,N’‐di(3’,3”,5’,5”‐tetrakis(4‐carboxyphenyl))‐1,2,6,7‐tetrachloroperylene‐3,4,9,10‐tetracarboxylic acid diimide (Cl‐PDI‐TA) and use it to successfully synthesize a novel Zr(IV)‐based MOF 1 constructed from [Zr 6 O 8 (H 2 O) 8 ] 8+ clusters bridged by Cl‐PDI‐TA ligands. Structural analysis revealed that Zr‐MOF 1 manifests a 3D framework with (4,8)‐connected csq topology and possesses triangular channels of ~17 Å and mesoporous hexagonal channels of ~26 Å along c ‐axis. Moreover, the synthesized Zr‐MOF 1 exhibits visible‐light absorption and efficient photoinduced free radical generation property, making it a promising photocatalytic molecular reactor. When Zr‐MOF 1 was used as a photocatalyst for the aerobic oxidation of sulfides under irradiation of visible light, it could afford the corresponding sulfoxides with high yield and selectivity. Experimental results demonstrated that the substrate sulfides could be fixed in the pores of 1 and directly transformed to the products sulfoxides in the solid state. Furthermore, the mechanism for the photocatalytic transformation was also investigated and the results revealed that the singlet oxygen ( 1 O 2 ) and superoxide radical (O 2 ⋅ − ) generated by the energy transfer and electron transfer from the photoexcited Zr‐MOF to oxidants were the main active species for the catalytic reactions. This work offers a perceptive comprehension of the mechanism in PDI‐based MOFs for further study on photocatalytic reactions.