RUI: Photochemistry and Photophysics of Macrocyclic Chromium(III) Complexes: An Investigation of Electronic Energy Self-Exchange

无机化学、生物无机化学和金属有机化学项目的这一RUI奖支持福尔曼大学的Paul S.Wagenkeck教授更好地了解同类物种之间的能量转移，以及热力学对近热中和能量转移反应的影响。例如反式[Cr(N4)(CN)2]+络合物(其中N4=四氮杂大环配体)，其热中能量传递可能比吸热或放热对应的至少快一个数量级，将被研究。新的几种类型的大环铬(III)络合物(有些具有可调的激发态性质)将被用于能量转移研究，以回答以下问题：发生这种速率峰值的能量区域有多窄？这种现象有多普遍？如何解释温度中和情况下的加速率？取代氰化物配体，将使用取代苯乙炔配体，以便可以通过取代苯乙炔来调节光行为。用脉冲激光激发和Stern-Volmer分析表征了新配合物的光物理性质和能量传递性质。该项目将提供与替代能源领域相关的基础数据，并将让本科生参与基础光化学研究。

This RUI award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports Professor Paul S. Wagenknecht at Furman University to develop a better understanding of energy transfer between like species and the effect of thermodynamics on nearly thermoneutral energy transfer reactions. Systems such as trans- [Cr(N4)(CN)2]+ complexes (where N4 = a tetraazamacrocylic ligand), in which the thermoneutral energy transfers may be at least an order of magnitude faster than either of their endothermic or exothermic counterparts, will be studied. New macrocyclic Cr(III) complexes (some with tunable excited state properties) of several types will be prepared and utilized in energy transfer studies to answer the following questions: How narrow is the energy region over which this spike in rate occurs? How general is this phenomenon? What is the explanation for the accelerated rate in the thermoneutral case? In place of the cyanide ligand, substituted phenylacetylide ligands will be employed so that the photobehavior can be tuned via substitutions on the phenylacetylide. The new complexes will be characterized as to their photophysics and energy transfer properties by using pulsed-laser excitation and Stern-Volmer analyses. This project will provide fundamental data relevant to the field of alternative energy sources and will involve undergraduates in basic photochemical research.