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

在我们对分子光响应性的量子放大感兴趣的背景下，研究了两种不同类型的反应系统。一种是萘基萘的光化学行为，基于一个涉及绝热光化学过程和能量转移的机制，期望进行芳构化。然而，光芳构化是逐步进行的，不涉及任何绝热组分，在苯二烯和萘二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，发现(1)2在室温下的稳态光解提供萘作为唯一产物，(2)从^12^*到^13^*存在绝热分数，(3)^32^*不发生价异构化，(4)没有具体的迹象表明从^12^*到^13^*的过程存在。研究的另一种类型的化学扩增是电子转移是传播的关键机制的系统。本课题研究了用三苯基吡啶离子进行光电子转移引发的四基[3.2.0.0^< 2,7 >0^< 4,6 >]庚烷(Q)及其衍生物的光致异构化反应。在这些反应体系中发生了非常有效的增殖，在一个情况下，产物形成的表观量子产率超过180。

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.