Mechanistic and Exploratory Organic Photochemistry

我们的总体目标是研究光化学机制，并发展新的光化学机制方法学。需要研究的具体问题如下：(1)一些与()酮平行的烯丙烯重排的研究()，(2)寻找镜像过程，其中涉及()激发，(3)完成Bugtriyne的合成和研究，Bugtriyne是一种具有三个乙烯桥的双环Mobius式分子，(4)Bugtriyne的六炔类化合物的合成和研究，(5)使用手性猝灭剂来确定沿反应坐标的物种是否受到能量转移的影响，(6)我们在固态光化学方面的继续努力和控制固态介质的方法，(7)对我们所研究的许多反应的超表面的研究，包括理论方法的比较，(8)继续我们的能量转移研究，使用我们合成的棒状分子来确定我们是否真的有sigma激子转移，(9)在SCF_CI计算中利用键定向基组轨道给出对有机化学研究有意义的结果，(10)测试我们对量子力学结果的处理以评估光化学反应中的能量局域化和扩散，(11)探索乙烯基环丙烯的“C”三重排重排，以确定区域选择性并揭示双自由基环扩张的机理，(12)确定酰基环丙烯以及亚胺和硫酮的重排机理，(13)探索反应多重数“交换积分控制”的共性和来源；(14)发展新的光化学概念。

Our overall aim is to study photochemical mechanisms and to develop new photochemical mechanistic methodology. Among the specific problems to be investigated are the following: (1) A study of some allene rearrangements which appear parallel to ( ) ketone counterparts ( ), (2) a search for the mirror image process, where a ( ) excited is involved, (3) completion of the synthesis and study of bugatriyne, a bicyclic Mobius type of molecule with three acetylenic bridges, (4) synthesis and study of the hexa-yne relative of bugatriyne, (5) use of chiral quenchers to determine whether species along the reaction coordinate are subject to energy transfer, (6) continuation of our efforts on solid state photochemistry and means of controlling the solid state medium, (7) investigation of hypersurfaces for many of the reactions we have studied, including a comparison of the theoretical methods, (8) continuing our energy transfer studies using the rod-like molecules we have synthesized to ascertain if we really do have sigma exciton transfer, (9) utilization of bond-oriented basis set orbitals in SCF_CI calculations to give results meaningful to organic chemical studies, (10) testing of our ( ) treatment to our quantum mechanical results to assess energy localization and diffusion during photochemical reaction, (11) exploration of the "Mechanism C" triplet rearrangement of vinylcyclopropenes to determine regioselectivity and to uncover the mechanisms of the diradical ring expansions, (12) determination of the mechanism of rearrangement of the acylcyclopropenes as well as imine and thione relatives, (13) investigation of the generality and sources of "Exchange Integral Control" of reaction multiplicity, (14) development of new photochemical concepts.