Ligand-Induced Direct Excitation Enables Deep-Red to Near-Infrared Nickel-Catalyzed C(sp ² )−C(sp ³ ) Cross-Coupling

We report a deep-red (DR)-to-near-infrared (NIR) light-driven Ni-catalyzed C(sp 2 )−C(sp 3 ) cross-coupling of alkylborons with aryl halides enabled by ligand-induced direct excitation of substrate−catalyst complexes. An aza-dipyrromethene catalyst forms a borate complex that directly absorbs DR−NIR light to trigger C−B bond cleavage and generate alkyl radicals while supporting productive nickel turnover under low-energy photons. Systematic optimization affords high yields under 660 nm irradiation and maintains efficient reactivity under 740 nm light. Broad substrate compatibility, including improved aryl chloride coupling, is achieved. Mechanistic studies delineate how photoexcited borate−nickel assemblies couple radical generation to catalytic bond construction, establishing a mechanistically grounded framework for DR−NIR nickel catalysis.