Novel Probes of Photochemical Mechanisms

结构，化学性质，光反应性，和新的 产生阴离子、稳定自由基和自由基的途径 离子将在这个项目中进行研究。结构将 通过比较这些中间体的溶液， 电化学相和固态核磁共振光谱 技术，并采用瞬态和稳态 作为激发态反应性的探针的照明。特别 利益将决定结构如何影响 酸性和氧化电位的几个家庭的 二价阴离子、自由基离子和稳定自由基。基本 热化学信息将通过关联速率获得 光化学和热电子转移与氧化还原 通过高速循环伏安法得到的电势，或 光调制伏安法探索新的推力 超临界流体中的光化学将寻求探索 在严格控制的条件下的溶剂化效应。在这些 研究，科学上重要的问题将探讨如何 聚集、环境和溶剂化影响化学 反应性，特别是电子转移反应。 有机动力学计划的这笔赠款支持 玛丽·安妮·福克斯教授在牛津大学的持续工作 德克萨斯州奥斯汀校区这项研究将产生一个 化学反应中间体的基本性质 反应.有机化学的机械论基础是 了解活性中间体的性质， 它们参与了化学转化。了解这些 中间体将使化学家更好地 预测化学反应的过程。

The structure, chemical properties, photoreactivity, and new routes for the generation of anions, stable radicals, and radical ions will be investigated in this project. Structure will be determined for these intermediates by a comparison of solution phase and solid state nmr spectroscopy, by electrochemical techniques, and by employing transient and steady state illumination as probes for excited state reactivity. Of particular interest will be the determination of how structure influences the acidities and oxidation potentials of several families of dianions, radical ions, and stable radicals. Fundamental thermochemical information will be attained by correlating rates of photochemical and thermal electron transfer with redox potentials derived by high speed cyclic voltammetry or photomodulation voltammetry. A new thrust exploring photochemistry in supercritical fluids will seek to probe solvation effects under carefully controlled conditions. In these studies, scientifically important questions will be probed of how aggregation, environment, and solvation affect chemical reactivity, particularly electron transfer reactions. This grant from the Organic Dynamics Program supports the continuing work of Professor Marye Anne Fox at the University of Texas, Austin Campus. This research will generate results of a fundamental nature about reactive intermediates in chemical reactions. The mechanistic basis of organic chemistry rests on an understanding of the properties of reactive intermediates and their involvement in chemical transformations. Knowledge of these intermediates will provide chemists with a better ability to predict the course of chemical reactions.