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New Development in Photochemistry of Molecules and Molecular Systems

分子与分子系统光化学新进展

基本信息

批准号：
03303001
负责人：
MIYASHI Tsutomu
金额：
$ 15.62万
依托单位：
TOHOKU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Co-operative Research (A)
财政年份：
1992
资助国家：
日本
起止时间：
1992 至 1993
项目状态：
已结题

项目摘要

In the fields of prganic and physical photochemistry of prganic molecues, cooperative researches between organic and physical chemists were extensively involved and following studies were performed and provided interesting results ; the first determination of rate constants for the C-C bond cleavage of ketone cation radicals, determination of the photoinduced CR Cope rearrangement mechanism, syntheses of various novel and practically useful photochromic molecules, difference in reactivities between ion radicals generated photochemically and under electron ionization, the photochemical generation of a novel TMM species, a new aspect of the Rehm-Weller relationship in a fluorescene quenching mechanism, novel electron-transfer reactions of azo compounds, dynamic studies on triplet biradicals from photoexcited cyclic ketones, determinations of the H-atom transfer mechanism via triplet exciplexes and the structure of triplet exciplexes, differences in reactivities between ion pairs and free ion radicals generated by photoinduced electron-transfer, and a novel photoinduced electron-transfer retro-Diels-Alder reactions of endoperoxides. In the field of photochemistry of inorganic and organometallic compounds, studies on photo-expoxidation of olefins using tetraphenylporphyrinatoantimony with water, time-resolved infrared and mossbauer spectroscopy of unstable organometallic intermediates, synthese and reactivities of matal-molecule clusters, photo-chemistry of peptide-porphyrin and photochemical properties of various photo-functionalized materials, were performed. The selective DNA cleavage using novel Photo-Fenton's regents was studied in bioorganic photo-chemistry. In the field of photochemistry of molecular systems, photodecomposition of NO_X by Cu^+/zeolite, application of porphyrin-polymer to photonics, a novel photochemical holeburning by two-color sensitization, reativities of organic molecules incorporated in LB layr composed of aromatic hydrocarbons

在有机分子的有机光化学和物理光化学领域，有机化学家和物理化学家的合作研究广泛开展，并取得了有趣的成果；酮离子自由基C-C键裂解速率常数的首次测定，光诱导CR - Cope重排机制的测定，各种新型和实用的光致变色分子的合成，光化学和电子电离下离子自由基反应性的差异，新型TMM物质的光化学生成，荧光猝灭机制中Rehm-Weller关系的新方面，偶氮化合物的新型电子转移反应，光激发环酮的三重态双自由基的动力学研究，通过三重态复合体和三重态复合体结构的h原子转移机制的测定，光诱导电子转移产生的离子对和自由基的反应性差异，以及内过氧化物的新型光诱导电子转移反- diels - alder反应。在无机和有机金属化合物的光化学领域，进行了四苯基卟啉锑与水的烯烃光氧化、不稳定有机金属中间体的时间分辨红外和穆斯堡尔光谱、材料-分子团簇的合成和反应性、肽-卟啉的光化学以及各种光功能化材料的光化学性质的研究。研究了新型光芬顿试剂在生物有机光化学中选择性切割DNA的作用。在分子体系光化学领域，研究了Cu^+/沸石对NO_X的光分解、卟啉聚合物在光子学中的应用、新型双色敏化光化学烧孔、有机分子掺入芳香烃LB层的反应性