Oxo-centered triruthenium clusters with carboxylic acid ancillary ligand form mixed valence dimers in solution upon reduction. Infrared spectroscopy shows localized behavior, indicating the exchange is slower than the vibrational timescale. UV/vis/NIR spectroscopy shows two IVCT bands that fit well with a semiclassical three state model for a moderately coupled class II system. The IVCT bands are closely related to molecular dimers of trimers systems with a bridging 4-4'-bipyridine. Low temperature electrochemistry clearly shows that dimerization is temperature dependent and that the hydrogen bonding interaction is dependent on the static dielectric constant of the solvent.

Proton dependent mixed valency in hydrogen bonded assemblies

245th National Meeting (2013)

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