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We demonstrate that several visible‐light‐mediated carbon−heteroatom cross‐coupling reactions can be carried out using a photoactive NiII precatalyst that forms in situ from a nickel salt and a bipyridine ligand decorated with two carbazole groups (Ni(Czbpy)Cl2). The activation of this precatalyst towards cross‐coupling reactions follows a hitherto undisclosed mechanism that is different from previously reported light‐responsive nickel complexes that undergo metal‐to‐ligand charge transfer. Theoretical and spectroscopic investigations revealed that irradiation of Ni(Czbpy)Cl2 with visible light causes an initial intraligand charge transfer event that triggers productive catalysis. Ligand polymerization affords a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross‐coupling reactions. The heterogeneous catalyst shows stable performance in a packed‐bed flow reactor during a week of continuous operation. [ABSTRACT FROM AUTHOR]

Flow Chemistry, Heterogeneous Catalysis, Homogeneous Catalysis, Photocatalysis, Nickel Catalysis Keywords: Flow Chemistry; Heterogeneous Catalysis; Homogeneous Catalysis; Photocatalysis; Nickel Catalysis EN Flow Chemistry Heterogeneous Catalysis Homogeneous Catalysis Photocatalysis Nickel Catalysis 1 1 1 11/09/22 20221114 NES 221114 B Intraligand charge transfer b activation of Ni(Czbpy)Cl SB 2 sb gives access to visible-light-mediated carbon-heteroatom cross-couplings in the absence of exogenous photocatalysts. Inside Back Cover: Intraligand Charge Transfer Enables Visible-Light-Mediated Nickel-Catalyzed Cross-Coupling Reactions (Angew. [Extracted from the article]