Abstract
The design of a biomimetic and fully base metal photocatalytic system for photocatalytic proton reduction in a homogeneous medium is described. A synthetic pyridylphosphole-appended [FeFe] hydrogenase mimic was encapsulated inside a supramolecular zinc porphyrin-based metal-organic cage structure Fe(4) (Zn-L)(6) . The binding is driven by the selective pyridine-zinc porphyrin interaction and results in the catalyst being bound strongly inside the hydrophobic cavity of the cage. Excitation of the capsule-forming porphyrin ligands with visible light while probing the IR spectrum confirmed that electron transfer takes place from the excited porphyrin cage to the catalyst residing inside the capsule. Light-driven proton reduction was achieved by irradiation of an acidic solution of the caged catalyst with visible light.