Reactive Intermediates and High Energy Molecules Related to Aromatic Photochemistry

有机动力学计划中的这笔拨款支持 Robert S博士的研究。谢里丹和独立党打交道 生成、分离、表征和反应性 在芳香族化合物中提出的高能中间体 光化学 一般的方法集中在综合和研究 这些活性中间体的前体。 主要目标是： (1)逐步阐明与之区别的因素 协同的热和光化学反应;（2）机理 芳族光加成的阐明;（3）新的， 芳香族化合物的高能前体;（4）检查 凝聚相中的“热分子”效应;（5）定义 对高度不稳定分子的观测极限 将合成高度放热的前体分子，其中 芳族部分形式上与小的、稳定的片段结合 例如CO、氮气和二氧化碳。化学发光 这些分子的绝热光致发光将是 当这些分子反应形成苯型结构时观察到。 分子光反应的光谱研究 兴趣将使用低温矩阵进行研究 隔离技术。

This grant in the Organic Dynamics Program supports the research of Dr.Robert S. Sheridan dealing with the independent generation, isolation, characterization and reactivity of energetic intermediates which have been proposed in aromatic photochemistry. The general approach centers on the synthesis and study of precursors to these reactive intermediates. Major goals are: (1) Elucidation of the factors distinguishing stepwise from concerted thermal and photochemical reactions; (2) Mechanistic elucidation of aromatic photoadditions; (3) Synthesis of novel, high-energy precursors to aromatic compounds; (4) Examination of "hot-molecule" effects in condensed phases; (5) Definition of the limits to the observation of highly unstable molecules. Highly exothermic precursor molecules will be synthesized where aromatic moieties are formally bound to small, stable fragments such as CO, nitrogen and carbon dioxide. The chemiluminescence and adiabatic photoluminescence of these molecules will be observed as these molecules react to form benzenoid structures. Spectroscopic studies of the photoreactions of the molecules of interest will be investigated using low temperature matrix isolation techniques.