Electro- and Photochemical Reduction of CO2 by Molecular Manganese Catalysts: Exploring the Positional Effect of Second-Sphere Hydrogen-Bond Donors

A series of molecular Mn catalysts featuring aniline groups in the second-coordination sphere has been developed for electrochemical and photochemical CO2 reduction. The arylamine moieties were installed at the 6 position of 2,2'-bipyridine (bpy) to generate a family of isomers in which the primary amine is located at the ortho- (1-Mn), meta- (2-Mn), or para-site (3-Mn) of the aniline ring. The proximity of the second-sphere functionality to the active site is a critical factor in determining catalytic performance. Catalyst 1-Mn, possessing the shortest distance between the amine and the active site, significantly outperformed the rest of the series and exhibited a 9-fold improvement in turnover frequency relative to parent catalyst Mn(bpy)(CO)(3)Br (901 vs. 102 s(-1), respectively) at 150 mV lower overpotential. The electrocatalysts operated with high faradaic efficiencies (>= 70 %) for CO evolution using trifluoroethanol as a proton source. Notably, under photocatalytic conditions, a concentration-dependent shift in product selectivity from CO (at high [catalyst]) to HCO2H (at low [catalyst]) was observed with turnover numbers up to 4760 for formic acid and high selectivities for reduced carbon products.

Automated summary

A series of molecular Mn catalysts with aniline groups were developed for electrochemical and photochemical CO2 reduction, with catalyst 1-Mn showing the highest efficiency. The proximity of the aniline groups to the active site is crucial in determining catalytic performance, with high faradaic efficiencies achieved using trifluoroethanol as a proton source and a shift in product selectivity observed under photocatalytic conditions.