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Development of Functional Dye for Molecular Optical-Information Conversion with Domino-type Amplification

多米诺放大分子光学信息转换功能染料的开发

基本信息

批准号：
12650834
负责人：
MIKI Sadao
金额：
$ 2.18万
依托单位：
Kyoto Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2002
项目状态：
已结题

项目摘要

In the context of our interest in quantum amplification of molecular photoresponsivity, two different type of reaction systems have been investigated.One is the photochemical behavior of naphthoylnaphthvalene with an expectation of propagating aromatization based on a mechanism involving an adiabatic photochemical process and an energy transfer. However, the photo-aromatization is stepwise and does not involve any adiabatic fractions, An adiabatic photo-reaction is reported in the case of benzvalene and naphthvalene (2). Thus, the present project reinvestigated photochemical behaviors of 2 to find out (1) steady state photolysis of 2 at room temperature affords naphthalene as a sole product, (2) there is an adiabatic fraction from ^12^* to ^13^*, (3) ^32^* does not undergo valence isomerization, (4) there is no concrete indication for the existence of the processes of from ^12^* to ^13^*.The other type of chemical amplification studied was the system in which electron transfer is a key mechanism for the propagation. The present project dealt with the photo-induced isomerization of tetracylo[3.2.0.0^<2, 7>0^<4, 6>]heptane (Q) and its derivative initiated with the photo-electron transfer by using triphenylpyrylium ion. Very efficient propagation occurred in these reaction systems, and in one case the apparent quantum yield for the product formation was over 180.

在我们对分子光响应量子放大的兴趣背景下，我们研究了两种不同类型的反应体系：一种是萘甲酰萘瓦烯的光化学行为，其预期的传播芳构化反应是基于一个包含绝热光化学过程和能量转移的机理;然而，光芳构化是逐步的，不涉及任何绝热馏分。在苯并瓦烯和萘并瓦烯的情况下，报道了绝热光反应（2）。因此，本项目重新研究了2的光化学行为，以发现（1）2在室温下的稳态光解提供萘作为唯一产物，（2）存在从^12^* 到^13^* 的绝热馏分，（3）^32^* 不发生价态异构化，（4）没有具体的迹象表明存在从^12 ^* 到^13 ^* 的过程。研究的另一种化学放大类型是电子转移是传播的关键机制的系统。本课题研究了三苯基吡喃离子引发的光电子转移引发的四[3.2.0.0^<2，7>0^<4，6>]庚烷（Q）及其衍生物的光诱导异构化反应。在这些反应体系中发生了非常有效的增长，在一种情况下，产物形成的表观量子产率超过180。