Nickel-Coordinated Carbon Nitride as a Metallaphotoredox Platform for the Cross-Coupling of Aryl Halides with Alcohols

Light-driven dual catalysis that combines photosensitizers and transition-metal complexes has become a powerful approach for diverse cross-coupling reactions. Heterogeneous photocatalysts recently have gained growing attention to build such catalytic system for controllable reaction kinetics and enhanced activity. Incorporating a metal catalyst into the framework of the photocatalyst could endow unique metallaphotoredox platforms. Herein, we assemble carbon nitride and nickel (C3N4–Ni) via direct coordination of Ni2+ to C3N4 nitrogen, for visible-light-driven carbon–oxygen cross-coupling. By operating with an imidazole auxiliary ligand, C3N4–Ni efficiently catalyzed etherification of a variety of aryl bromides with alcohols or hydroxylation with water, exhibiting turnover numbers of >500. Ni maintained as isolated single site without aggregation after photoreaction and the recovered catalyst demonstrate sustained activity without additional Ni loading. Our work signifies the potential of uniting dual catalysis in well-designed sensitizer–metal architecture for complex organic transformations.