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

这个RUI奖在无机，生物无机和有机化学计划支持教授保罗S。Wagenknecht在弗曼大学，以发展更好地了解类似物种之间的能量转移和热力学对近热中性能量转移反应的影响。 将研究诸如反式- [Cr（N4）（CN）2]+络合物（其中N4 =四氮杂大环配体）的系统，其中热中性能量转移可能比它们的吸热或放热对应物快至少一个数量级。 新的大环铬（III）配合物（一些可调激发态性能）的几种类型将被制备和利用在能量转移的研究，以回答以下问题：如何狭窄的能量区域，在此尖峰率发生？这种现象有多普遍？在热中性的情况下，加速率的解释是什么？ 取代的苯乙炔配体代替氰化物配体，使得可以通过苯乙炔上的取代来调节光行为。通过脉冲激光激发和Stern-Volmer分析，将新的配合物的物理和能量传递特性进行表征。该项目将提供与替代能源领域有关的基本数据，并将使本科生参与基本的光化学研究。

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.