Understanding the intricacies of inner sphere electron transfer has been a challenge for nearly 50 years. We employ the coalescence of ?(CO) bandshapes observed in the infrared (IR) spectra of mixed valence complexes of the type {[Ru3O(OAc)6(CO)(L)]2-BL}-1, where L = a pyridyl ligand and BL =  pyrazine, to determine electron transfer (ET) rates.  These studies revealed unusual behavior, including increasing rates of ET as the temperature is decreased, and failure to conform to several of the major tenets of the Marcus-Hush theory of electron transfer. We investigated ET across metallic nanoparticles using these systems, and obtained similar trends in ET rates. These studies of optical and ground state thermal ET in systems progressing through a localized-to-delocalized transition have provided generalized guidelines for establishing a new definition of the Class II/III borderline. We seek to extend our knowledge of these systems to study ET across nanoparticles, and hydrogen bonded systems.

Ultrafast electron transfer in supramolecular mixed valence systems

245th National Meeting (2013)

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