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- W2045125306 abstract "A series of binuclear complexes of general formula LmRu−BL−RuL‘mn+ where L and L‘ are monodentate or bidentate ligands bound to one metal center and BL is a bridging ligand are analyzed with the recently reported unified solvation model (USM). The solvent dependence of ΔE1/2 and EIT data are analyzed for cases where L is the same as L‘ and where L and L‘ differ. Data for the change in E1/2 and EIT as the Lewis base, B, is varied in (bpy)2ClRupyz Ru(NH3)4B (where bpy is 2,2‘-bipyridine and pyz is pyrazine) are also correlated. The USM provides the relative contributions of specific and nonspecific solvation to the solvent dependence of the physicochemical property. The factoring of the solvent dependence permits the construction of potential energy surfaces providing unprecedented detail concerning the influence of solvent donor−acceptor and solvation contributions to these measurements. The ability of USM to correlate Franck−Condon energies and the failure of donor numbers (DN) to do so emphasizes the need for a dual parameter treatment of the specific interaction. In contrast to nonsymmetrical binuclear complexes, the solvent dependence of the EIT bands for symmetrical complexes is not correlated by solvent donor and polarity parameters but is fit to the dielectric constants and refractive indices of the Marcus−Hush dielectric continuum model. A rationale for this disparate behavior of symmetrical and unsymmetrical binuclear complexes is given." @default.
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- W2045125306 date "1997-01-01" @default.
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- W2045125306 title "Specific and Nonspecific Solvation Contributions to Intervalence Electron Transfer Transitions and Redox Potentials in Ruthenium Ammine Complexes" @default.
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- W2045125306 doi "https://doi.org/10.1021/ic960066o" @default.
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