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Photo-induced Electron-relay Reaction Utilizing Electrostatic Field of Polymers

利用聚合物静电场的光致电子接力反应

基本信息

批准号：
63470072
负责人：
SAWAKI Yasuhiko
金额：
$ 3.26万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1989
项目状态：
已结题

项目摘要

Molecular aggregates are formed between polystyrenesulfonate anions (PSS^-) and stilbazolium cations (Stz^+) by means of their electrostatic interactions. A co-adsorbed sensitizer, Ru(bpy)_3^<2+> 2+ transfers, on irradiation, its electron into stilbazolium cation resulting in the formation of stylbazole radical. An efficient electron relay takes place among the olefin aggregates, and highly efficient cis to trans isomerization of the olefins occurs, quantum yields being as high as 100. Firstly, we could show that the thousands of Stz^+ ions bound to PSS^- are divided into small aggregates of micelle-like clusters and that their aggregation numbers are constant in the range of 80-90, irrespective of the degree of polymerization of PSS^-. The electron-relay chain isomerization proceeds within one micellar cluster. Secondly, we could succeed in detecting directly stylbazole radical, as an unstable transient intermediate in the cis-trans isomerization. Photolysis of a mixture of p-dicyanobenzene (DCB) and naphthalene in the presence of stilbazolium cation yielded a transient species, (^<lambda>max 420 nm) at the expense of anion radical of DCB (^<lambda>max 340 nm). The transient spectrum is that of stylbazole radical, and decays satisfying a second-order kinetics. The decay rate constant has been found to be heavily increased by the addition of polystyrenesulfonate anions, which implies that an electron is rapidly relayed among the adsorbed stilbazolium ion aggregates.

聚苯乙烯磺酸阴离子（PSS^-）和二苯唑离子（Stz^+）通过静电相互作用形成分子聚集体。一种共吸附的敏化剂Ru(bpy)_3^<2+ bbb_2 +在辐照下将其电子转移到二苯基唑阳离子中，从而形成丁苯唑自由基。烯烃聚集体之间发生了有效的电子接力，烯烃发生了高效的顺式到反式异构化，量子产率高达100。首先，我们可以证明，与PSS^-结合的数千个Stz^+离子被分成胶束状簇的小聚集体，并且它们的聚集数在80-90的范围内是恒定的，而与PSS^-的聚合程度无关。电子接力链异构化在一个胶束团簇内进行。其次，我们可以成功地直接检测到在顺反异构化过程中不稳定的瞬态中间体——基甲唑自由基。对二氨基苯（DCB）和萘的混合物在二氮唑阳离子存在下光解产生一个瞬态物质（^< λ >max 420 nm），而DCB的阴离子自由基（^< λ >max 340 nm）则被破坏。其瞬态谱为甲醚基谱，衰变符合二级动力学。发现聚苯磺酸阴离子的加入大大增加了衰变速率常数，这意味着电子在吸附的二苯唑离子聚集体之间迅速传递。