Catalytic Water Oxidation by Ruthenium Complexes Containing Negatively Charged Ligand Frameworks

Artificial photosynthesis represents an attractive way of converting solar energy into storable chemical energy. The H₂O oxidation half‐reaction, which is essential for producing the necessary reduction equivalents, is an energy‐demanding transformation associated with a high kinetic barrier. Herein we present a couple of efficient Ru‐based catalysts capable of mediating this four‐proton‐four‐electron oxidation. We have focused on the incorporation of negatively charged ligands, such as carboxylate, phenol, and imidazole, into the catalysts to decrease the redox potentials. This account describes our work in designing Ru catalysts based on this idea. The presence of the negatively charged ligands is crucial for stabilizing the metal centers, allowing for light‐driven H₂O oxidation. Mechanistic details associated with the designed catalysts are also presented.