Organic Photochemistry Induced by Visible and Infrared Irradiation and in Unusual Environments

这个更新奖是在有机动力学计划，以支持玛丽安妮福克斯博士的研究。 本研究将探讨其结构、化学性质、光反应性，以及产生稳定自由基、双自由基、自由基离子和卡宾的新途径。 将通过溶液相和固态NMR光谱的比较、电化学技术以及激发态反应性的瞬态和稳态光化学探针来确定结构。 结构对光诱导电子转移效率的影响以及长波长可见光或红外光是否能引发新的光反应性将被探索。 从一个共同的激发态的竞争反应途径之间的选择性分配的相位和局部环境的影响将被研究。 这项工作将集中在理解典型的光化学行为的差异引起的限制在一个大小受限的沸石，在自组装单层，在分子固体，并在超临界流体中的光活性分子。 对有机化学中关键反应的理解依赖于对反应中间体的性质、稳定性和结构的了解。 这些知识是需要了解的光吸附有机染料的机械化学的有效利用，分子导体，半导体和磁铁的设计，在表面改性催化剂的合成，并作为一种工具，了解控制化学反应性的聚集效应。 f8-？ ; + S um m m ary in for m m a t i o n ( ++++++++++++ ( Û ++++++++++++ ++++++++++++ ++++++++++++ + 你好，我的天啊 Ý + ] $ H L + ¢ ╗ D H + ++++++++++++++++++++++++++++++++ R:\WWUSER\TEMPLATE\NORMAL.DOT

This renewal award is made in the Organic Dynamics Program in support of the research of Dr. Marye Anne Fox. The structure, chemical properties, photoreactivity, and new routes for the generation of stable radicals, biradicals, radical ions and carbenes will be investigated. Structure will be established by a comparison of solution phase and solid state NMR spectroscopy, by electrochemical techniques, and by transient and steady state photochemical probes for excited state reactivity. The effect of structure on the efficiency of photoinduced electron transfer and whether novel photoreactivity can be initiated by long wavelength visible or infared light will be explored. The effect of phase and local environment on selective partitioning among competing reaction pathways from a common excited state will be studied. This work will focus on understanding differences in typical photochemical behavior elicited by constraining a photoactive molecule within a size-constrained zeolite, within a self-assembled monolayer, within molecular solids, and in supercritical fluids. Progress in understanding the key reactions organic chemistry depends on the knowledge of the properties, stabilities and structures of reactive intermediates. Such knowledge is required for understanding the efficient utilization of light-adsorptive organic dyes in mechanistic chemistry, for the design of molecular conductors, semiconductors, and magnets, in the synthesis of surface-modified catalysts, and as a vehicle for understanding aggregation effects in controlling chemical reactivity. f8 Û-ª þ ; + S u m m a r y I n f o r m a t i o n ( ++++++++++++ ( Û ++++++++++++ ++++++++++++ ++++++++++++ + Ûª▓ ÑOh ª' +'ª▒0 Ý + ] $ H l + ¢ ╗ D h + ++++++++++++++++++++++++++++++++ R:\WWUSER\TEMPLATE\NORMAL.DOT