Intervalence involvement of bridging ligand vibrations in hexaruthenium mixed-valence clusters probed by resonance Raman spectroscopy |
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Authors: | Londergan Casey H Rocha Reginaldo C Brown Mac G Shreve Andrew P Kubiak Clifford P |
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Affiliation: | Department of Chemistry, University of California-San Diego, 9500 Gilman Drive, Mail Code 0358, La Jolla, CA 92093-0358, USA. |
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Abstract: | Resonance Raman spectroscopy, performed using spectroelectrochemistry and with excitation in the intervalence bands of three pyrazine-bridged, mixed-valence dimers of trinuclear ruthenium clusters, shows resonant enhancement of symmetric bridging ligand modes. The resonant enhancements and frequency shifts of these bridging ligand modes are observed as a function of varying electronic communication between charge sites, and they show that a three-state vibronic model which explicitly includes the participation of the bridging ligand is needed to explain the spectroscopic behavior of these near-delocalized complexes. |
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