Metallaphotocatalytic cross-coupling reactions are typically carried out by combining homogeneous or heterogeneous photocatalysts with a soluble nickel complex. Previous attempts to realize recyclable catalytic systems use immobilized iridium complexes to harvest light. We present bifunctional materials based on semiconductors for metallaphotocatalytic C−S cross-coupling reactions that can be reused without losing their catalytic activity. Key to the success is the permanent immobilization of a nickel complex on the surface of a heterogeneous semiconductor through phosphonic acid anchors. The optimized catalyst harvests a broad range of the visible light spectrum and requires a nickel loading of only ∼0.1 mol %.
