Hydrogen Evolution by Fe III Molecular Electrocatalysts Interconverting between Mono and Di-Nuclear Structures in Aqueous Phase

A new FeL/Fe L manifold, with HL=2-({[di(2-pyridyl)methyl](methyl)amino}methyl)phenol, was prepared in gram scale (>50 % yield) and characterized in solution and solid state. The monomer/dimer interconversion is controlled in aqueous phase, upon varying the pH conditions. The electrocatalytic hydrogen evolution reaction (HER) occurs through the FeL monomer with added trifluoroacetic acid (TFA) and through the Fe L μ-oxo dimer in acetate buffer (pH 4.9), with an overpotential of about 1 V and faradaic yield up to 75 %. The resulting i /i values in the range 15-28 are among the highest reported for Fe-based electrocatalysts (i is the catalytic current, whereas i is the current of an Fe-based redox event).