Photochemistry of Cumulenes and Asymmetric Photochemistry

这项有机和高分子化学方面的拨款为新汉普郡大学理查德·约翰逊博士的研究提供了支持。这项工作的重点是有机化合物的选择性光化学反应的机理。这种反应在视觉过程中很重要，并形成了许多工业应用的基础。将研究几个基本问题。第一个涉及一类被称为累积烯的分子，它含有多个圆周率键。具体目标包括对已知反应的详细机理研究，对合成新的和复杂结构的可能性的调查，以及对新型累积烯的探索性实验。第二个重点是不对称光反应，即那些在有机化合物中产生或修饰手性的反应。将开展研究手性在能量转移、手性联芳基反应和圆偏振光应用方面的实验。此外，从头算量子力学方法将应用于光化学反应中的瞬时中间体的研究。一项具体的研究涉及反式苯，一种新的C6H6异构体，它可能是许多鲜为人知的苯光化学的关键。

This grant in Organic and Macromolecular Chemistry provides support for the research of Dr. Richard Johnson, University of New Hampshire. The work is focused on the mechanisms of selected photochemical (light-induced) reactions of organic compounds. Such reactions are important in the visual process and form the basis of numerous industrial applications. Several fundamental problems will be studied. The first concerns a class of molecules known as cumulenes, which contain multiple pi bonds. Specific goals include detailed mechanistic studies of known reactions, investigation of the potential for synthesis of new and complex structures, and exploratory experiments with new types of cumulenes. A second emphasis is on asymmetric photoreactions, that is those which generate or modify chirality in organic compounds. Experiments to study chirality in energy transfer, reactions of chiral biaryls, and applications of circularly polarized light will be carried out. In addition, ab initio quantum mechanical methods will be applied to the study of transient intermediates in photchemical reactions. One specific investigation concerns trans-benzene, a new C6H6 isomer, which may be the key to much of the poorly understood photochemistry of benzene.