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Cyclometalated Ir-Zr-MOFs as Recyclable Visible-Light Photocatalysts for Sulfide Oxidation into Sulfoxide in Water.

08:00 EDT 11th October 2019 | BioPortfolio

Summary of "Cyclometalated Ir-Zr-MOFs as Recyclable Visible-Light Photocatalysts for Sulfide Oxidation into Sulfoxide in Water."

Aerobic photo-oxidation of sulfide into sulfoxide in water is of great interest in synthesis chemistry. In this study, three high stable Ir(III)-Zr(IV) metal-organic frameworks (Ir-Zr-MOFs), namely Zr6-Irbpy (bpy is 2,2'-bipyridine), Zr6-IrbpyOMe (bpyOMe is 4,4'-dimethoxy-2,2'-bipyridine), and Zr6-Irphen (phen is 1,10-phenanthroline), are constructed by using [Ir(pqc)2(L)2]Cl complexes (where pqc is 2-phenylquinoline-4-carboxylic acid, L is an ancillary ligand bpy, bpyOMe or phen) as linkers and Zr6 cluster as nodes. The constructed Ir-Zr-MOFs present high catalytic activity on aerobic photo-oxidation of sulfide into sulfoxide under visible light irradiation in water at room temperature. Moreover, the reaction is high chemoselectivity and functional group tolerance. The catalyst can be readily recycled and reused at least ten times without loss of catalytic activity. Mechanism studies demonstrate that superoxide radical is the reactive oxygen species in the sulfoxidation, which is generated by electron transfer from the excited triplet photosensitizer 3[Ir-Zr-MOF]* to O2. The high activity of photocatalytic sulfoxidation in water may be attributed to the sta-bilization of the persulfoxide intermediate by hydrogen bonds formation with water solvent, which accelerates the conversion of persulfoxide into sulfoxide and prevents further oxidation of sulfoxide into sulfone. This work provides a new strategy for green synthesis of sulfoxides using MOF as photosensitizer under ambient conditions.

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Name: ACS applied materials & interfaces
ISSN: 1944-8252
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