Photocatalytic CO₂ reduction using (Cu₂-Metallacycle) mediated by phenyl–pentafluorophenyl interaction

Three isostructural binuclear Cu₂-metallacycles were synthesized using flexible (N^N)-(N^N) ligands with varied spacer lengths to precisely modulate the intramolecular Cu···Cu distance. These Cu₂-metallacycles were assembled with a Ru(N^N)₃-photosensitizer via phenyl–pentafluorophenyl interactions. The different Cu₂-metallacycles displayed distinct photocatalytic CO₂ reduction performances, demonstrating how microstructural modulation of otherwise isostructural architectures influences catalytic behavior. Notably, photocatalytic activity was greatly enhanced when a pentafluorophenyl-containing photosensitizer was employed, owing to improved charge-transfer capability. This work aims to provide reference and inspiration for exploring the impact of complex microstructure regulation on catalytic performance and for developing charge-transfer pathways in dual-catalyst systems.