Electronic effects promoted the catalytic activities of binuclear Co(ii) complexes for visible-light-driven CO2 reduction in a water-containing system

Abstract

Under the action of a catalyst, the photoinduced reduction of CO₂ to chemicals and fuels is one of the greenest and environment-friendly approaches for decreasing atmospheric CO₂ emissions. Since the environment was affected by the greenhouse effect, scientists have never stopped exploring efficient photoinduced CO₂ 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 [Co₂(L¹)(OAc)₂](OAc) (Co₂L¹, HL¹ = 2,6-bis((bis(pyridin-2-ylmethyl)amino)methyl)-4-methoxyphenol), which accelerates the visible-light-driven conversion of CO₂ to CO in acetonitrile/water (4/1, v/v) nearly 40% more than that for the previously reported [Co₂(L²)(OAc)₂](OAc) (Co₂L², HL² = 2, 6-bis((bis(pyridin-2-ylmethyl)amino)methyl)-4-(tert-butyl)phenol) by our research group. It has an excellent CO selectivity of 98%, and the TON_CO 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 (–OCH₃) in Co₂L¹ compared to a tertiary butyl group (–C(CH₃)₃) in Co₂L², which reduces the energy barrier of the rate-limiting CO₂ coordination step in the visible-light-driven CO₂ reduction process.