Reactive Intermediates and High Energy Molecules Related to Aromatic Photochemistry

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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.