Electronic effects promoted the catalytic activities of binuclear Co(II) complexes for visible-light-driven CO reduction in a water-containing system.

Under the action of a catalyst, the photoinduced reduction of CO to chemicals and fuels is one of the greenest and environment-friendly approaches for decreasing atmospheric CO emissions. Since the environment was affected by the greenhouse effect, scientists have never stopped exploring efficient photoinduced CO reduction systems, particularly the highly desired non-noble metal complexes. Most of the currently reported complexes based on non-noble metals exhibit low catalytic activity, selectivity, and stability in aqueous systems under the irradiation of visible light. Herein, we report a new binuclear cobalt complex Co(L)(OAc) (Co2L1, HL = 2,6-bis((bis(pyridin-2-ylmethyl)amino)methyl)-4-methoxyphenol), which accelerates the visible-light-driven conversion of CO to CO in acetonitrile/water (4/1, /) nearly 40% more than that for the previously reported Co(L)(OAc) (Co2L2, HL = 2, 6-bis((bis(pyridin-2-ylmethyl)amino)methyl)-4-(-butyl)phenol) by our research group. It has an excellent CO selectivity of 98%, and the TON is as high as 5920. Experimental results and DFT calculations showed that the enhanced catalytic performance of Co2L1 is due to the electron-donating effect of a methoxy group (-OCH) in Co2L1 compared to a tertiary butyl group (-C(CH)) in Co2L2, which reduces the energy barrier of the rate-limiting CO coordination step in the visible-light-driven CO reduction process.