Rhenium Carbonyl Molecular Catalysts for CO₂ Electroreduction: Effects on Catalysis of Bipyridine Substituents Mimicking Anchorage Functions to Modify Electrodes

Heterogenization of molecular catalysts on (photo)­electrode surfaces is required to design devices performing processes enabling to store renewable energy in chemical bonds. Among the various strategies to immobilize molecular catalysts, direct chemical bonding to conductive surfaces presents some advantages because of the robustness of the linkage. When the catalyst is, as it is often the case, a transition metal complex, the anchoring group has to be connected to the complex through the ligands, and an important question is thus raised on the influence of this function on the redox and on the catalytic properties of the complex. Herein, we analyze the effect of conjugated and non conjugated substituents, structurally close to anchoring functions previously used to immobilize a rhenium carbonyl bipyridyl molecular catalyst for supported CO₂ electroreduction. We show that carboxylic ester groups, mimicking anchoring the catalyst via carboxylate binding to the surface, have a drastic effect on the catalytic activity of the complex toward CO₂ electroreduction. The reasons for such an effect are revealed via a combined spectro-electrochemical analysis showing that the reducing equivalents are mainly accumulated on the electron-withdrawing ester on the bipyridine ligand preventing the formation of the rhenium(0) center and its interaction with CO₂. Alternatively, alkyl-phosphonic ester substituents, not conjugated with the bpy ligand, mimicking anchoring the catalyst via phosphonate binding to the surface, allow preserving the catalytic activity of the complex.