Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers

► The redox potentials of both centers in these dinuclear complexes can be adjusted smoothly. ► In solution, these complexes exhibit an intense solvent-dependent MM′CT (RuII → FeIII) absorption in the near infrared region. ► Analysis of this band in systems suggests an enhanced communication as the energies of the metal centers come closer. ► The spectroscopy of anion trans-[(dmap)5Ru(μ-NC)Fe(CN)5]− (dmap = 4-dimethylaminopyridine) in water indicates a Ru(III)-Fe(II) character.