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

该奖项在无机，生物无机和有机化学计划支持博士Clifford P. Kubiak在圣地亚哥的加州大学研究红外（IR）光谱的动态平均现象通过超快电子转移（ET）在价间电荷转移复合物。 通过对实验可调参数（配体、溶剂等）的系统研究，将确定控制ET速率和振动光谱动态平均的关键因素。 通过电子交换对红外光谱进行动态平均的光谱学研究，以完成该现象的自洽物理图像，并测试现有电子转移理论在弱定域和完全离域行为之间的知之甚少的阈值处的可靠性。 第一个研究比较电子转移和空穴转移类似的协调复杂的框架内进行。 新的合成研究将针对复合物，可用于研究通过超分子组装和扩展固态材料的极快的电荷转移。 了解电子转移过程的起源，它们的动力学，以及可以从分子系统扩展到散装材料的关系，反之亦然，触及电子转移至关重要的几个重要的生物和技术系统。 该研究将继续通过UCSD本科生研究导师计划参与本科生男性和女性。 该项目还将与加州大学圣地亚哥分校现有的外展计划对接，以招募代表性不足的群体进入博士学位。程序.

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.