Mixed Valency in Inorganic Chemistry: Synthetic Control, Dynamics, and Extension to Supramolecular Assemblies

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This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Dr. Clifford P. Kubiak at the University of California at San Diego to study the phenomenon of dynamical averaging of infrared (IR) spectra by ultrafast electron transfer (ET) in intervalence charge transfer complexes. Through systematic studies of experimentally adjustable parameters (ligands, solvent, etc) the crucial factors controlling ET rates and dynamical averaging of vibrational spectra will be defined. Spectroscopic studies of dynamical averaging of IR spectra by electron exchange will be undertaken to complete a self-consistent physical picture of the phenomenon, and to test the reliability of existing theories of electron transfer at the poorly understood threshold between weakly localized and fully delocalized behavior. The first studies to compare electron transfer and hole transfer within similar coordination complex frameworks will be undertaken. New synthetic studies will be directed toward complexes that can be used to study extremely rapid charge transfers through supramolecular assemblies, and over extended solid state materials. Understanding the origins of electron transfer processes, their dynamics, and the relationships that can be extended from molecular systems to bulk materials, and vice versa, touch on several of the important biological and technological systems where electron transfer is vital. The research will continue to involve undergraduate men and women through the UCSD undergraduate research mentor program. The project will also be interfaced with existing outreach programs at UCSD for the recruitment of underrepresented groups into Ph. D. programs.