Intervalence involvement of bridging ligand vibrations in hexaruthenium mixed-valence clusters probed by resonance Raman spectroscopy.
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.
Londergan
Casey H
CH
Department of Chemistry, University of California-San Diego, 9500 Gilman Drive, Mail Code 0358, La Jolla, CA 92093-0358, USA.
Rocha
Reginaldo C
RC
Brown
Mac G
MG
Shreve
Andrew P
AP
Kubiak
Clifford P
CP