Supramolecular bimetallic assemblies for photocatalytic hydrogen generation from water

A series of supramolecular assemblies of the type [Ru(L-L)₂(L′-L)MX₂)]ⁿ⁺ are reported where L-L is 2,2′-bipyridine (bipy), 4,4′-di-tetra-butyl-bipyridine (tbbipy) or 4,4′-diethoxycarbonyl-2,2′-bipyridine (dceb), L-L′ is tetrapyrido[3,2-a:2′,3′-c:3′′,2′′-h:2′′′,3′′′-j]phenazine (tpphz), 2,2′:5′,2′′-terpyridine (2,5-bpp), 2,2′:6′,2′′-terpyridine, (2,6-bpp), 2,5-di(pyridine-2-yl)pyrazine (2,5-dpp) or 2,3-di(pyridine-2-yl)pyrazine (2,3-dpp), and MX₂ is PdCl₂, PtCl₂ or PtI₂. The photocatalytic behaviour with respect to hydrogen generation of these compounds and their ultrafast photophysical properties are discussed as a function of the nature of the peripheral ligands, the bridging ligands and the catalytic centre. The results obtained show how differences in the chemical composition of the photocatalysts can affect intramolecular photoinduced electron transfer processes and the overall photocatalytic efficiency.