Metal–Organic Layers as Multifunctional Two-Dimensional Nanomaterials for Enhanced Photoredox Catalysis

Metal–organic layers (MOLs) have recently emerged as a novel class of molecular two-dimensional (2D) materials with significant potential for catalytic applications. Herein we report the design of a new multifunctional MOL, Hf 12 -Ir-Ni, by laterally linking Hf 12 secondary building units (SBUs) with photosensitizing Ir(DBB)[dF(CF 3 )ppy] 2 + [DBB-Ir-F, DBB = 4,4′-di(4-benzoato)-2,2′-bipyridine; dF(CF 3 )ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine] bridging ligands and vertically terminating the SBUs with catalytic Ni(MBA)Cl 2 [MBA = 2-(4′-methyl-[2,2′-bipyridin]-4-yl)acetate] capping agents. Hf 12 -Ir-Ni was synthesized in a bottom-up approach and characterized by TEM, AFM, PXRD, TGA, NMR, ICP-MS, UV–vis, and luminescence spectroscopy. The proximity between photosensitizing Ir centers and catalytic Ni centers (∼0.85 nm) in Hf 12 -Ir-Ni facilitates single electron transfer, leading to a 15-fold increase in photoredox reactivity. Hf 12 -Ir-Ni was highly effective in catalytic C–S, C–O, and C–C cross-coupling reactions with broad substrate scopes and turnover numbers of ∼4500, ∼1900, and ∼450, respectively.