Recyclable Perovskite/g-C3N4 Heterojunction Enabling Photo-redox Nickel-Catalyzed C(sp2)-C(sp3) Cross-Electrophile Coupling

Nickel-catalyzed cross-electrophile coupling (XEC) provides an efficient and cost-effective strategy for constructing C(sp ² )-C(sp ³ ) bonds, a pivotal transformation for diversifying molecular architectures in pharmaceutical and agrochemical synthesis. However, conventional XEC methodologies usually require stoichiometric metal reductants, which pose safety risks, reaction instability, and environmental concerns. To circumvent these limitations, merging nickel catalysis with photoredox catalysis has emerged as a promising alternative. Central to this approach is to develop highly efficient, easy-to-prepare and recyclable photocatalysts, which can drive the reaction under mild conditions. In this work, we present a recyclable LaFeO ₃ /LaCoO ₃ /g-C ₃ N ₄ heterojunction. The stepped band structure and dual Z-scheme carrier migration paths significantly enhance photocatalytic performance by synergistically increasing redox potentials and extending the lifetime of photogenerated charge carriers through efficient interfacial charge transfer. Leveraging this heterojunction, we have developed a nickel/photoredox dual-catalyzed XEC between aryl iodides and alkyl halides, eliminating the need for stoichiometric metal reductants. This catalytic system demonstrates broad compatibility with diverse aryl iodides and alkyl halides, affording the desired products with up to 98% yields. The perovskite/g-C ₃ N ₄ photocatalyst enables quantitative catalyst recovery and maintains consistent activity over 5 cycles (> 90% yield), substantially improving process sustainability. Mechanistic studies reveal that photogenerated electrons from the heterojunction simultaneously mediate both alkyl halide activation and nickel catalyst reduction.