Metal-Organic Layers with Photosensitizer and Pyridine Pairs Activate Alkyl Halides for Photocatalytic Heck-Type Coupling with Olefins.

Photochemical generation of alkyl radicals from haloalkanes often requires strong energy input from ultraviolet light or a strong photoreductant. Haloalkanes can alternatively be activated with nitrogen-based nucleophiles through a sequential SN2 reaction and single-electron reduction to access alkyl radicals, but these two reaction steps have opposite steric requirements on the nucleophiles. Herein, we report the design of Hf12 metal-organic layers (MOLs) with iridium-based photosensitizer bridging ligands and secondary-building-unit-supported pyridines for photocatalytic alkyl radical generation from haloalkanes. By bringing the photosensitizer and pyridine pairs in proximity, the MOL catalysts allowed facile access to the pyridinium salts from SN2 reactions between haloalkanes and pyridines and at the same time enhanced electron transfer from excited photosensitizers to pyridinium salts to facilitate alkyl radical generation. Consequentially, the MOLs efficiently catalyzed Heck-type cross-coupling reactions between haloalkanes and olefinic substrates to generate functionalized alkenes. The MOLs showed 4.6 times higher catalytic efficiency than the homogeneous counterparts and were recycled and reused without a loss of catalytic activity.

Sequential Modifications of Metal-Organic Layer Nodes for Highly Efficient Photocatalyzed Hydrogen Atom Transfer.

Herein, we report the synthesis of a bifunctional photocatalyst, Zr-OTf-EY, through sequential modifications of metal cluster nodes in a metal-organic layer (MOL). With eosin Y and strong Lewis acids on the nodes, Zr-OTf-EY catalyzes cross-coupling reactions between various C-H compounds and electron-deficient alkenes or azodicarboxylate to afford C-C and C-N coupling products, with turnover numbers of up to 1980. In Zr-OTf-EY-catalyzed reactions, Lewis acid sites bind the alkenes or azodicarboxylate to increase their local concentrations and electron deficiency for enhanced radical additions, while EY is stabilized by site isolation on the MOL to afford a long-lived catalyst for hydrogen atom transfer. The proximity between photostable EY sites and Lewis acids on the nodes of Zr-OTf-EY enhances the catalytic efficiency by approximately 400 times over the homogeneous counterpart in the cross-coupling reactions.