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

这一续展奖项是在有机动力学项目中颁发的，以支持Marye Anne Fox博士的研究。将研究其结构、化学性质、光反应性以及生成稳定的自由基、双自由基、自由基离子和卡宾的新途径。结构将通过比较溶液相和固态核磁共振波谱，通过电化学技术，以及通过激发态反应性的瞬时和稳态光化学探针来确定。将探索结构对光诱导电子转移效率的影响，以及长波可见光或红外光是否能引发新的光反应。将研究相和局域环境对从共同激发态到竞争反应路径的选择性分配的影响。这项工作将集中于了解通过将光活性分子限制在尺寸受限的沸石中、在自组装单分子层中、在分子固体中以及在超临界流体中所引起的典型光化学行为的差异。在理解关键反应有机化学方面的进展取决于对反应中间体的性质、稳定性和结构的了解。这些知识对于理解光吸附有机染料在机械化学中的有效利用，对于分子导体、半导体和磁体的设计，在表面修饰催化剂的合成中，以及作为一种媒介来理解控制化学反应的聚集效应，都是必需的。F8；+S(++$H L+，╗D h+

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