Mechanistic and Exploratory Organic Photochemistry

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The following research projects will be pursued: (1) Continued general exploration for examples where unimolecular photochemistry in the unit cell of a crystal differs from that in solution, (2) The search for more examples where two crystalline modifications with different space groups differ in reactivity, (3) "Crystal Engineering" by use of patterned surfaces to effect nucleation of different space group crystals, (4) Development of quantitative methods correlating crystal reactivity with prediction, (5) "Spiderweb Photochemistry" of molecules entrapped in cross-linked polymers, (6) The design of product-shaped cavities leading reactants to desired products (i.e., synthetic enzymes), (7) A study of chiral quenchers of achiral excited state reactants, (8) Development of a molecular clock to determine triplet rates, (9) Theoretical treatments of organic reactions, and (10) Development of new photochemical concepts. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Howard E. Zimmerman at the University of Wisconsin. Molecules will be excited with light to produce excited states where the resulting reactions will be studied in detail. Included in this study will be: (1) experiments to uncover new photochemical reactions, (2) new ways to control excited state reactivity, (3) the development of new techniques in photochemistry. Some of the projects will envolve the use of crystal and polymer cavities to tailor photochemical reactions, the use of specially designed molecules to time excited state processes, and the theoretical treatment of reactions of organic molecules.