JULIEN BONIN

Inspired by natural enzymes, this study presents a nickel‐based molecular catalyst, [Ni ‖ (N 2 S 2 )]Cl 2 ( NiN 2 S 2 , N 2 S 2 =2,11‐dithia[3,3](2,6)pyridinophane), for the photochemical catalytic reduction of CO 2 under visible light. The catalyst was synthesized and characterized using various techniques, including liquid chromatography‐high resolution mass spectrometry (LC‐HRMS), UV‐Visible spectroscopy, and X‐ray crystallography. The crystallographic analysis revealed a slightly distorted octahedral coordination geometry with a mononuclear Ni 2+ cation, two nitrogen atoms and two sulfur atoms. Photocatalytic CO 2 reduction experiments were performed in homogeneous conditions using the catalyst in combination with [Ru(bpy) 3 ]Cl 2 (bpy=2,2’‐bipyridine) as a photosensitizer and 1,3‐dimethyl‐2‐phenyl‐2,3‐dihydro‐1 H ‐benzo[ d ]imidazole (BIH) as a sacrificial electron donor. The catalyst achieved a high selectivity of 89 % towards CO and a remarkable turnover number (TON) of 7991 during 8 h of visible light irradiation under CO 2 in the presence of phenol as a co‐substrate. The turnover frequency (TOF) in the initial 6 h was 1079 h −1 , with an apparent quantum yield (AQY) of 1.08 %. Controlled experiments confirmed the dependency on the catalyst, light, and sacrificial electron donor for the CO 2 reduction process. These findings demonstrate this bioinspired nickel molecular catalyst could be effective for fast and efficient photochemical catalytic reduction of CO 2 to CO.