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We report the electronic spectrum of the prototypical ruthenium coordination complex Ru(bpy)32+ (bpy = 2,2'-bipyridine) by messenger tagging with N2 in a cryogenic ion trap and photodissociation spectroscopy of mass selected Ru(bpy)32+·N2 ions. We observe individual electronic bands and groups of bands with unprecedented detail, particularly in the usually unresolved metal-to-ligand charge transfer region of the spectrum. By comparing our experimental results with time-dependent density functional theory, both with and without spin-orbit interaction [Heully et al., J. Chem. Phys. 131, 184308 (2009)], we are able to assign the spectrum of the isolated ion. [ABSTRACT FROM AUTHOR]

We report the electronic spectra of mass selected [(bpy)(tpy)Ru-OH2]2+·(H2O)n clusters (bpy = 2,2′-bipyridine, tpy =2,2′:6′2″-terpyridine, n = 0-4) in the spectral region of their metal-to-ligand charge transfer bands. The spectra of the mono- and dihydrate clusters exhibit partially resolved individual electronic transitions. The water network forming at the aqua ligand leads to a rapid solvatochromic shift of the peak of the band envelope: addition of only four solvent water molecules can recover 78% of the solvatochromic shift in bulk solution. The sequential shift of the band shows a clear change in behavior with the closing of the first hydration shell. We compare our experimental data to density function theory (DFT) calculations for the ground and excited states. [ABSTRACT FROM AUTHOR]