Abstract
A system for visible light-driven hydrogen production from water is reported. This system makes use of a synthetic mini-enzyme known as a mimochrome (CoMC6*a) consisting of a cobalt deuteroporphyrin and two attached peptides as a catalyst, [Ru(bpy)(3)](2+) (bpy = 2,2'-bipyridine) as a photosensitizer, and ascorbic acid as a sacrificial electron donor. The system achieves turnover numbers (TONs) up to 10,000 with respect to catalyst and optimal activity at pH 7. Comparison with related systems shows that CoMC6*a maintains the advantages of biomolecular catalysts, while exceeding other cobalt porphyrins in terms of total TON and longevity of catalysis. Herein, we lay groundwork for future study, where the synthetic nature of CoMC6*a will provide a unique opportunity to tailor proton reduction chemistry and expand to new reactivity.