STUDIES ON THE STRUCTURE OF PARAMAGNETIC UNSTABLE CHEMICAL SPECIES AND KINETICS OF THE FORMATION AND REACTION

本次合作研究是在以下五个小标题下进行的，通过讨论和交流有关顺磁性不稳定物种的化学信息。在三年的任期内，共举办了三次研讨会，约有100名成员，其中包括26名主要研究者。(1)通过时间分辨ESR光谱对顺磁物质的形成和反应进行动力学研究：使用一些机构提供的时间分辨ESR系统，研究了许多光化学反应。结果包括三重态-三重态能量转移过程中的自旋极化守恒，瞬态辐射对的观测，以及光诱导质子或氢转移反应。激发三重态是该分支的另一个重要课题。(2)顺磁激发态分子的电子态和弛豫：激发态三重态分子的电子态、三重态子能级内的自旋极化和光化学反应顺序。 ...更多信息 介绍了芳香族硝基化合物、氮杂芳香族化合物、邻醌类化合物和芳香族羰基化合物。研究了有机自由基晶体的反铁磁性质。(3)凝聚相中不稳定顺磁物质的结构与反应：该分支的研究成果包括饱和烃阳离子自由基的电子结构、分子运动和反应，有机高自旋分子的分子内自旋排列，环糊精包合自由基等。(4)顺磁性金属配合物和有机金属化合物的结构与反应：用ESR和ENDOR技术研究了顺磁性金属配合物和铜配合物的结构和自旋状态，以及硅基和锗基自由基的结构和自旋状态。光化学也是该领域的热门课题。(5)生物学上重要的顺磁物质的形成、结构和反应：研究了生物系统中活性氧自由基的检测。本文首次用ESR和自旋捕集技术研究了近紫外光引起的眼透镜中的自由基。金属离子在生物系统中的功能是另一个主题。本课题研究报告共提交研究报告277份。少

This co-operative research was carried out under the following five subtitles through discussions and exchanging informations about the chemistry of paramagnetic unstable species. Three seminars were held during the 3-years term and about 100 members including 26 main investigators were concerned with this project.(1) Kinetic studies on the formation and reaction of paramagnetic species by means of time- resolved ESR spectroscopy : Using time-resolved ESR systems facilitated in some institutions, many photochemical reactions were investigated. The results include- spin polarization conservation during triplet-triplet energy transfer, observation of transient radital pair, and photoinduced proton or hydrogen transfer reactions. Excited triplet state was another big subject in this branch.(2) Electronic state and relaxation of paramagnetic excited molecules: Electronic state of excited triplet molecules, spin polarization within a triplet sublevels, and sequence for photochemiahl reactio … More ns were dealt with aromatic nitro compounds, azaaromatics, o-quinones, and aromatic carbonyl compounds. Antiferromagnetic property of organic radical crystal was also investigated.(3) Structure and reaction of unstable paramagnetic species trapped in condensed phase: Results in this branch include the studies on the electronic structure, molecular motion, and reaction of saturated hydrocarbon cation radicals, intramolecular spin alignment in organic high-spin molecules, and free radicals included into cyclodextrin.(4) Structure and reaction of paramagnetic metal complexes and organometallic compounds: Structure and spin state of rhenium complexes and copper complexes, silyl and germyl radicals were studied by means of ESR and ENDOR techniques. Photochemistry is also current topics in this field.(5) Formation, structure, and reaction of biologically important paramagnetic species: Detection of active oxygen radicals in biological systems was studied. Near ultraviolet induced free radicals in ocular lens were first investigated by ESR and spin trapping. Function of metal ions in biological systems were another subject . 277 Research reports were filed in the report of this project research. Less