A Planar‐Structured Dinuclear Cobalt(II) Complex with Indirect Synergy for Photocatalytic CO2‐to‐CO Conversion

Abstract Dinuclear metal synergistic catalysis (DMSC) has been proved an effective approach to enhance catalytic efficiency in photocatalytic CO 2 reduction reaction, while it remains challenge to design dinuclear metal complexes that can show DMSC effect. The main reason is that the influence of the microenvironment around dinuclear metal centres on catalytic activity has not been well recognized and revealed. Herein, we report a dinuclear cobalt complex featuring a planar structure, which displays outstanding catalytic efficiency for photochemical CO 2 ‐to‐CO conversion. The turnover number (TON) and turnover frequency (TOF) values reach as high as 14457 and 0.40 s −1 respectively, 8.6 times higher than those of the corresponding mononuclear cobalt complex. Control experiments and theoretical calculations revealed that the enhanced catalytic efficiency of the dinuclear cobalt complex is due to the indirect DMSC effect between two Co II ions, energetically feasible one step two‐electron transfer process by Co 2 I,I intermediate to afford Co 2 II,II (CO 2 2− ) intermediate and fast mass transfer closely related with the planar structure.