Reactive Intermediates and High Energy Molecules Related to Aromatic Photochemistry

这项有机动力学项目资助了robert S. Sheridan博士在芳香光化学中提出的高能中间体的独立生成、分离、表征和反应性方面的研究。一般的方法集中在合成和研究这些反应中间体的前体。主要目标是：(1)阐明逐步区别于协同热化学反应和光化学反应的因素；(2)芳香光加成的机理研究；(3)新型高能芳香族化合物前体的合成；(4)凝聚态中“热分子”效应的检验；(5)确定高度不稳定分子的观测范围。高度放热的前体分子将在芳香族部分与CO、氮和二氧化碳等小而稳定的片段正式结合的地方合成。当这些分子反应形成苯类结构时，将观察到这些分子的化学发光和绝热光发光。对感兴趣的分子的光反应的光谱研究将使用低温基质分离技术进行研究。

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.