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

无机化学、生物无机化学和金属有机化学项目的这一奖项支持加州大学圣地亚哥分校的Clifford P.Kubiak博士研究通过超快电子转移(ET)在价间电荷转移络合物中动态平均红外(IR)光谱的现象。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。将通过电子交换对红外光谱的动态平均进行光谱研究，以完成这一现象的自洽物理图像，并测试现有电子转移理论的可靠性，这些理论的电子转移在弱局域行为和完全离域行为之间的阈值知之甚少。将在类似的配位络合物框架内进行第一次比较电子转移和空穴转移的研究。新的合成研究将指向可用于研究超分子组件和扩展的固态材料中极快速的电荷转移的络合物。理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块状材料的关系，反之亦然，涉及到几个重要的生物和技术系统，其中电子转移是至关重要的。这项研究将继续通过加州大学圣迭戈分校的本科生研究导师计划让本科生男性和女性参与。该项目还将与加州大学圣迭戈分校现有的外展计划相结合，以招募代表人数不足的群体进入博士项目。

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.