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

Author:

Chen Jia‐Qi1,Zhang Kai‐Yang1,Zhang Xiu‐Du2ORCID,Huang Zi‐Qing1,Deng Hong1,Zhao Yue1ORCID,Shi Zhuang‐Zhi1,Sun Wei‐Yin1ORCID

Affiliation:

1. Coordination Chemistry Institute State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering Nanjing National Laboratory of Microstructures Collaborative Innovation Center of Advanced Microstructures Nanjing University Nanjing 210023 P. R. China

2. College of Chemistry and Materials Science Key Laboratory of Functional Molecular Solids Ministry of Education Anhui Laboratory of Molecule-Based Materials Anhui Key Laboratory of Functional Molecular Solids Anhui Normal University Wuhu 241002 P. R. China

Abstract

AbstractThe 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 [Zr6O8(H2O)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 (1O2) and superoxide radical (O2) 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.

Funder

National Natural Science Foundation of China

Publisher

Wiley

Subject

General Chemistry,Catalysis,Organic Chemistry

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