Supramolecules Containing Homogeneous Electron‐rich Cu Sites for Photocatalytic CO₂ Reduction to C₂H₆

Abstract Light‐driven CO₂ reduction to multi‐carbon (C₂₊) products is ideal but remains challenging. This paper anchors the metal active center on the electron‐rich capabilities 4‐(diphenylamine)‐thiophene carboxylic acid supramolecular receptor unit. Then a novel supramolecular catalyst that satisfies the optimal distance of C–C coupling is constructed utilizing the π‐conjugated group stacking effect. The activity of this catalyst is superior to most photocatalysts reported for the reduction of CO₂ to C₂H₆, with a C₂H₆ yield of 250.9 µmol h⁻¹ g⁻¹, a selectivity of 64.2%. In situ spectroscopic and theoretical calculations demonstrate that the photogenerated electrons accumulate at the adjacent metal active center, thereby effectively CO₂ activation and ^*CO capture. This process reduces the reaction energy barrier of C–C coupling. In addition, constructing controllable and homogeneous Cu active sites improved the selectivity of CO₂ reduction to C₂H₆. This study provides a new way to design photocatalysts with precisely controllable electron‐enriched metal active sits to realize photo‐driven reduction of CO₂ to C₂₊ products.