Issue 48, 2012

Mixed-valence state of symmetric diruthenium complexes: synthesis, characterization, and electron transfer investigation

Abstract

Complexes of the type {[(pyS)Ru(NH3)4]2-μ-L}n, where pyS = 4-mercaptopyridine, L = 4,4′-dithiodipyridine (pySSpy), pyrazine (pz) and 1,4-dicyanobenzene (DCB), and n = +4 and +5 for fully reduced and mixed-valence complexes, respectively, were synthesized and characterized. Electrochemical data showed that there is electron communication between the metal centers with comproportionation constants of 33.2, 1.30 × 108 and 5.56 × 105 for L = pySSpy, pz and DCB, respectively. It was also observed that the electronic coupling between the metal centers is affected by the π-back-bonding interaction toward the pyS ligand. Raman spectroscopy showed a dependence of the intensity of the vibrational modes on the exciting radiations giving support to the assignments of the electronic transitions. The degree of electron communication between the metal centers through the bridging ligands suggests that these systems can be molecular wire materials.

Graphical abstract: Mixed-valence state of symmetric diruthenium complexes: synthesis, characterization, and electron transfer investigation

Supplementary files

Article information

Article type
Paper
Submitted
01 Mar 2012
Accepted
26 Sep 2012
First published
03 Oct 2012

Dalton Trans., 2012,41, 14540-14546

Mixed-valence state of symmetric diruthenium complexes: synthesis, characterization, and electron transfer investigation

S. D. O. Pinheiro, T. D. F. Paulo, D. D. S. de Abreu, E. Longhinotti, C. H. B. Silva, G. F. S. Andrade, M. L. A. Temperini and I. C. N. Diógenes, Dalton Trans., 2012, 41, 14540 DOI: 10.1039/C2DT32092D

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