Photocatalytic Hydrogen Evolution Driven by a Heteroleptic Ruthenium(II) Bis(terpyridine) Complex

Since the initial report by Lehn et al. in 1979, ruthenium tris(bipyridine) ([Ru(bpy)3]2+) and its numerous derivatives were applied as photosensitizers (PSs) in a large panel of photocatalytic conditions while the bis(terpyridine) analogues were disregarded because of their low quantum yields and short excited-state lifetimes. In this study, we prepared a new terpyridine ligand, 4'-(4-bromophenyl)-4,4‴:4″,4‴'-dipyridinyl- 2,2':6',2″-terpyridine (Bipytpy) and used it to prepare the heteroleptic complex [Ru(Tolyltpy)(Bipytpy)](PF6)2 (1; Tolyltpy = 4'-tolyl-2,2':6',2'-terpyridine). Complex 1 exhibits enhanced photophysical properties with a higher quantum yield (7.4 × 10-4) and a longer excited-state lifetime (3.8 ns) compared to those of [Ru(Tolyltpy)2](PF6)2 (3 × 10-5 and 0.74 ns, respectively). These enhanced photophysical characteristics and the potential for PS-catalyst interaction through the peripheral pyridines led us to apply the complex for visible-light-driven hydrogen evolution. The photocatalytic system based on 1 as the PS, triethanolamine as a sacrificial donor, and cobaloxime as a catalyst exhibits sustained activity over more than 10 days under blue-light irradiation (light-emitting diode centered at 450 nm). A maximum turnover number of 764 was obtained after 12 days.