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Issue 48, 2012
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Mixed-valence state of symmetric diruthenium complexes: synthesis, characterization, and electron transfer investigation

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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

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Publication details

The article was received on 01 Mar 2012, accepted on 26 Sep 2012 and first published on 03 Oct 2012


Article type: Paper
DOI: 10.1039/C2DT32092D
Citation: Dalton Trans., 2012,41, 14540-14546
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    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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