Mechanistic and Exploratory Organic Photochemistry

将继续进行以下研究项目：(1)继续一般性探索晶体晶胞中的单分子光化学与溶液中的单分子光化学不同的例子，(2)寻找更多具有不同空间群的两种晶体修饰在反应性上不同的例子，(3)通过使用图案化表面来影响不同空间群晶体的成核，(4)将晶体反应性与预测联系起来的定量方法的发展，(5)交联型聚合物中分子的“蜘蛛网光化学”，(6)将反应物引向所需产物(即合成酶)的产物形腔的设计，(7)非手性激发态反应物的手性猝灭剂的研究，(8)确定三重态速率的分子钟的发展，(9)有机反应的理论处理，以及(10)新的光化学概念的发展。来自有机动力学项目的这笔赠款支持威斯康星大学霍华德·E·齐默尔曼教授的继续工作。分子将被光激发以产生激发态，在那里产生的反应将被详细研究。这项研究将包括：(1)发现新的光化学反应的实验，(2)控制激发态反应性的新方法，(3)光化学新技术的发展。其中一些项目将涉及使用晶体和聚合物腔来定制光化学反应，使用特殊设计的分子来计算激发态过程的时间，以及有机分子反应的理论处理。

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.