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We report the design of a bifunctional metal–organic layer (MOL), Hf₁₂‐Ru‐Co, composed of [Ru(DBB)(bpy)₂]²⁺[DBB‐Ru, DBB=4,4′‐di(4‐benzoato)‐2,2′‐bipyridine; bpy=2,2′‐bipyridine] connecting ligand as a photosensitizer and Co(dmgH)₂(PPA)Cl (PPA‐Co, dmgH=dimethylglyoxime; PPA=4‐pyridinepropionic acid) on the Hf₁₂secondary building unit (SBU) as a hydrogen‐transfer catalyst. Hf₁₂‐Ru‐Co efficiently catalyzed acceptorless dehydrogenation of indolines and tetrahydroquinolines to afford indoles and quinolones. We extended this strategy to prepare Hf₁₂‐Ru‐Co‐OTf MOL with a [Ru(DBB)(bpy)₂]²⁺photosensitizer and Hf₁₂SBU capped with triflate as strong Lewis acids and PPA‐Co as a hydrogen transfer catalyst. With three synergistic active sites, Hf₁₂‐Ru‐Co‐OTf competently catalyzed dehydrogenative tandem transformations of indolines with alkenes or aldehydes to afford 3‐alkylindoles and bisindolylmethanes with turnover numbers of up to 500 and 460, respectively, illustrating the potential use of MOLs in constructing novel multifunctional heterogeneous catalysts.

We report the design of a bifunctional metal–organic layer (MOL), Hf₁₂‐Ru‐Co, composed of [Ru(DBB)(bpy)₂]²⁺[DBB‐Ru, DBB=4,4′‐di(4‐benzoato)‐2,2′‐bipyridine; bpy=2,2′‐bipyridine] connecting ligand as a photosensitizer and Co(dmgH)₂(PPA)Cl (PPA‐Co, dmgH=dimethylglyoxime; PPA=4‐pyridinepropionic acid) on the Hf₁₂secondary building unit (SBU) as a hydrogen‐transfer catalyst. Hf₁₂‐Ru‐Co efficiently catalyzed acceptorless dehydrogenation of indolines and tetrahydroquinolines to afford indoles and quinolones. We extended this strategy to prepare Hf₁₂‐Ru‐Co‐OTf MOL with a [Ru(DBB)(bpy)₂]²⁺photosensitizer and Hf₁₂SBU capped with triflate as strong Lewis acids and PPA‐Co as a hydrogen transfer catalyst. With three synergistic active sites, Hf₁₂‐Ru‐Co‐OTf competently catalyzed dehydrogenative tandem transformations of indolines with alkenes or aldehydes to afford 3‐alkylindoles and bisindolylmethanes with turnover numbers of up to 500 and 460, respectively, illustrating the potential use of MOLs in constructing novel multifunctional heterogeneous catalysts.

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 Ir^IIIphotoredox catalyst and a Ni^IIcross‐coupling catalyst into a stable Zr₁₂MOF, Zr₁₂‐Ir‐Ni, to efficiently catalyze C−S bond formation between various aryl iodides and thiols. The proximity of the Ir^IIIand Ni^IIcatalytic 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.

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 Ir^IIIphotoredox catalyst and a Ni^IIcross‐coupling catalyst into a stable Zr₁₂MOF, Zr₁₂‐Ir‐Ni, to efficiently catalyze C−S bond formation between various aryl iodides and thiols. The proximity of the Ir^IIIand Ni^IIcatalytic 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.