A layered lead halide framework intercalated with Ru(bpy)3 for efficient CO2 photoreduction

Three-dimensional lead halide hybrids exhibit excellent photophysical properties but suffer from inherent instability. In contrast, two-dimensional layered lead halides offer enhanced environmental stability, yet their strongly bound excitons restrict efficient charge transport. Here we present a covalent intercalation strategy involving the benchmark photosensitizer [Ru(bpy) 3 ] 2+ into a layered lead halide framework, featuring cationic [Pb 23 X 42 ] 4+ (X −  = Cl − or Br − ) layers pillared by [Ru(bpy) 3 ] 2+ ligands via Pb 2+ -carboxylate coordination. This hybrid material achieves nearly full visible-light absorption and efficient photoinduced charge transfer from [Ru(bpy) 3 ] 2+ to the lead halide layers. This affords efficient CO 2 -to-CO photoreduction with an apparent quantum efficiency of ~3.0% at 500 nm, exceeding the performance of all previously reported organolead halide photocatalysts. Mechanistic studies indicate that the [Ru(bpy) 3 ] 2+ ligands enhance charge transport to Pb 2+ sites, facilitating CO 2 activation and reducing the reaction barrier for the *COOH intermediate. This work establishes a paradigm for intercalation chemistry in robust layered lead halide hybrids.