Merging Photoredox and Organometallic Catalysts in a Metal–Organic Framework Significantly Boosts Photocatalytic Activities

Metal–organic frameworks (MOFs) have been extensively used for single‐site catalysis and light harvesting, but their application in multicomponent photocatalysis is unexplored. We report here the successful incorporation of an IrIII photoredox catalyst and a NiII cross‐coupling catalyst into a stabl...

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Published inAngewandte Chemie International Edition Vol. 57; no. 43; pp. 14090 - 14094
Main Authors Zhu, Yuan‐Yuan, Lan, Guangxu, Fan, Yingjie, Veroneau, Samuel S., Song, Yang, Micheroni, Daniel, Lin, Wenbin
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 22.10.2018
EditionInternational ed. in English
Subjects
Aromatic compounds
Catalysis
Catalysts
heterogeneous catalysis
Iodides
Metal-organic frameworks
Metals
nickel
Photocatalysis
photochemistry
sulfides
Thiols
nickel
heterogeneous catalysis
photochemistry
metal-organic frameworks
sulfides
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Summary:Metal–organic frameworks (MOFs) have been extensively used for single‐site catalysis and light harvesting, but their application in multicomponent photocatalysis is unexplored. We report here the successful incorporation of an IrIII photoredox catalyst and a NiII cross‐coupling catalyst into a stable Zr12 MOF, Zr12‐Ir‐Ni, to efficiently catalyze C−S bond formation between various aryl iodides and thiols. The proximity of the IrIII and NiII catalytic components to each other (ca. 0.6 nm) in Zr12‐Ir‐Ni greatly facilitates electron and thiol radical transfers from Ir to Ni centers to reach a turnover number of 38 500, an order of magnitude higher than that of its homogeneous counterpart. This work highlights the opportunity in merging photoredox and organometallic catalysts in MOFs to effect challenging organic transformations. Business merger: The incorporation of both an IrIII photoredox catalyst and a NiII cross‐coupling catalyst into a stable Zr12 metal–organic framework (MOF) affords a solid dual photocatalyst for C−S coupling between aryl iodides and thiols. By facilitating electron and thiophenol radical transfers from Ir to Ni centers, the MOF photocatalyst exhibits an order of magnitude higher catalytic activity than its homogeneous counterpart.
Bibliography:These authors contributed equally to this work.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201809493