Early photophysical events of a ruthenium(ii) molecular dyad capable of performing photochemical water oxidation and of its model compounds

The early photophysical events occurring in the dinuclear metal complex [(ttb-terpy)(I)Ru(μ-dntpz)Ru(bpy)2]3+ (2; ttb-terpy = 4,4',4''-tri-tert-butyl-terpy; bpy = 2,2'-bipyridine; dntpz = 2,5-di-(1,8-dinaphthyrid-2-yl)pyrazine) - a species containing the chromophoric (bpy)2Ru(μ-dntpz)2+ subunit and the catalytic (I)(ttb-terpy)Ru(μ-dntpz)+ unit, already reported to be able to perform photocatalytic water oxidation - have been studied by ultrafast pump-probe spectroscopy in acetonitrile solution. The model species [Ru(bpy)2(dntpz)]2+ (1), [(bpy)2Ru(μ-dntpz)Ru(bpy)2]4+ (3), and [(ttb-terpy)(I)Ru((μ-dntpz)Ru[(ttb-terpy)(I)]2+ (4) have also been studied. For completeness, the absorption spectra, redox behavior of 1-4 and the spectroelectrochemistry of the dinuclear species 2-4 have been investigated. The usual 3MLCT (metal-to-ligand charge transfer) decay, characterized by relatively long lifetimes on the ns timescale, takes place in 1 and 3, whose lowest-energy level involves a (bpy)2Ru(dntpz)2+ unit, whereas for 2 and 4, whose lowest-energy excited state involves a 3MLCT centered on the (I)(ttb-terpy)Ru(μ-dntpz)+ subunit, the excited-state lifetimes are on the ps timescale, possibly involving population of a low-lying 3MC (metal-centered) level. Compound 2 also exhibits a fast process, with a time constant of 170 fs, which is attributed to intercomponent energy transfer from the MLCT state centered in the (bpy)2Ru(μ-dntpz)2+ unit to the MLCT state involving the (I)(ttb-terpy)Ru(μ-dntpz)+ unit. Both the intercomponent energy transfer and the MLCT-to-MC activation process take place from non-equilibrated MLCT states.