Abstract

We report here the synthesis and properties of a family of mixed-valence cyanide-bridged dinuclear complex ions trans-[(L′L4RuII(μ-NC)FeIII(CN)5]− (with L=pyridine or 4-dimethylaminopyridine (dmap) and L′=pyridine, 4-methoxypyridine (meopy) or 4-dimethylaminopyridine)) whose properties could be adjusted smoothly by changing the acceptor properties of the solvent and the σ donor properties of the L′ pyridine ligand. In solution these complexes exhibit an intense solvent-dependent MM′CT (RuII→FeIII) absorption in the near infrared region. Analysis of this band in different complexes and solvents suggests an enhanced interaction as the energies of the metal centers come closer. From this trend the anion trans-[(dmap)5Ru(μ-NC)Fe(CN)5]− (dmap=4-dimethylaminopyridine) in water is expected to belong to the class II-III, but its spectral properties indicates a ground state with Ru(III)–Fe(II) character. The stabilization of this electronic isomer is probably related to the better donor properties of the hexacyanoferrate(II) moiety and its stronger interaction with water.

Talk to us

Join us for a 30 min session where you can share your feedback and ask us any queries you have

Schedule a call

Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.