Abstract
The prototypical [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine, Ru-1) with 3MLCT state (metal-to-ligand charge-transfer, πM → πL*) is one of the most widely used photosensitizers (PSs) for photocatalytic hydrogen production. However, its photostability and excited state lifetime (<1 μs) are eagerly to be improved to further enhance the performance of hydrogen production. Herein, [Ru(bpy)2(3-pyrenyl-1,10-phenanthroline)]2+ (Ru-3) with 3IL/3MLCT equilibrated state and [Ru(bpy)2(3-pyrenyl ethynylene-1,10-phenanthroline)]2+(Ru-4) with 3IL state (intraligand charge transfer, πL → πL*) as lowest excited state were first introduced into the photocatalytic hydrogen evolution system. Photophysical and photocatalytic characteristics manifest that the 3IL state complex (Ru-4) shows a long-lived excited state (up to 120 μs) and much enhanced photostability with no photobleaching over 13 h in stark contrast to Ru-1 and [Ru(bpy)2(1,10-phenanthroline)]2+ (Ru-2). Photocatalytic reactions with these Ru(II) complexes as PSs, Co(dmgH...
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