Single-Site Photocatalytic H₂ Evolution from Covalent Organic Frameworks with Molecular Cobaloxime Co-Catalysts

We demonstrate photocatalytic hydrogen evolution using COF photosensitizers with molecular proton reduction catalysts for the first time. With azine-linked N2-COF photosensitizer, chloro(pyridine)cobaloxime co-catalyst, and TEOA donor, H₂ evolution rate of 782 μmol h^-1 g^-1 and TON of 54.4 has been obtained in a water/acetonitrile mixture. PXRD, solid-state spectroscopy, EM analysis, and quantum-chemical calculations suggest an outer sphere electron transfer from the COF to the co-catalyst which subsequently follows a monometallic pathway of H₂ generation from the Co^III-hydride and/or Co^II-hydride species.