Bioinspired cobalt cubanes with tunable redox potentials for photocatalytic water oxidation and CO reduction.

The development of efficient, robust and earth-abundant catalysts for photocatalytic conversions has been the Achilles' heel of solar energy utilization. Here, we report on a chemical approach based on ligand designed architectures to fabricate unique structural molecular catalysts coupled with appropriate light harvesters (e.g., carbon nitride and Ru(bpy)) for photoredox reactions. The "CoO" cubane complex CoO(COMe)(RNCH) (R = CN, Br, H, Me, OMe), serves as a molecular catalyst for the efficient and stable photocatalytic water oxidation and CO reduction. A comprehensive structure-function analysis emerged herein, highlights the regulation of electronic characteristics for a molecular catalyst by selective ligand modification. This work demonstrates a modulation method for fabricating effective, stable and earth-abundant molecular catalysts, which might facilitate further innovation in the function-led design and synthesis of cubane clusters for photoredox reactions.