Mechanistic and Exploratory Organic Photochemistry

我们的总体目标是研究光化学机理，发展新的光化学机理方法。需要研究的具体问题有：(1)研究了一些平行于（）酮对应物（）的烯重排（），(2)寻找了涉及（）激发的镜像过程，(3)完成了双环Mobius型分子bugatriyne的合成和研究，bugatriyne具有三个乙炔桥，(4)合成和研究了bugatriyne的六炔亲戚。(5)使用手性猝灭剂来确定沿着反应坐标的物质是否会受到能量转移的影响；(6)继续我们在固态光化学和控制固态介质方面的努力；(7)研究我们研究过的许多反应的超表面，包括理论方法的比较；(8)利用我们合成的棒状分子继续我们的能量转移研究，以确定我们是否真的有sigma激子转移；(9)在SCF_CI计算中利用键取向基集轨道，为有机化学研究提供有意义的结果；（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定位和扩散；（11）探索乙烯基环丙烯的“机制C”三重重排，以确定区域选择性，并揭示双基环扩张的机制；（12）确定酰基环丙烯以及亚胺和硫酮的重排机制，（13）研究反应多样性的“交换积分控制”的普遍性和来源，（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.