Site Isolation in Metal-Organic Layers Enhances Photoredox Gold Catalysis

Herein, we report the synthesis of a metal-organic layer, Hf-Ru-Au, containing Ru(bipyridine)₃²⁺-type photosensitizers and (phosphine)-AuCl catalysts for photoredox Au-catalyzed cross-coupling of allenoates, alkenes, or alkynes with aryldiazonium salts to afford furanone, tetrahydrofuran, or aryl alkyne derivatives, respectively. Site isolation of (phosphine)-AuCl complexes in Hf-Ru-Au prevents Au catalyst deactivation via ligand redistribution, Au(I) disproportionation, and aryl-phosphine reductive elimination, while the proximity between the Ru photosensitizers and Au catalysts enhances catalytic efficiency, with 14-200 times higher activity over those of the homogeneous controls in the cross-coupling reactions.