Photocatalytic Hydrogen Evolution by a Synthetic [FeFe] Hydrogenase Mimic Encapsulated in a Porphyrin Cage.

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 Fe4 (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.