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

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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