Dinuclear manganese complexes for water oxidation: evaluation of electronic effects and catalytic activity

During recent years significant progress has been made towards the realization of a sustainable and carbon-neutral energy economy. One promising approach is photochemical splitting of H 2 O into O 2 and solar fuels, such as H 2 . However, the bottleneck in such artificial photosynthetic schemes is the H 2 O oxidation half reaction where more efficient catalysts are required that lower the kinetic barrier for this process. In particular catalysts based on earth-abundant metals are highly attractive compared to catalysts comprised of noble metals. We have now synthesized a library of dinuclear Mn 2 II,III catalysts for H 2 O oxidation and studied how the incorporation of different substituents affected the electronics and catalytic efficiency. It was found that the incorporation of a distal carboxyl group into the ligand scaffold resulted in a catalyst with increased catalytic activity, most likely because of the fact that the distal group is able to promote proton-coupled electron transfer (PCET) from the high-valent Mn species, thus facilitating O-O bond formation. A library of dinuclear Mn-based water oxidation catalysts demonstrates that distal, non-innocent groups in the ligand framework enhance their catalytic efficiency.