Investigation of Electronic-State Dependence of Photoreaction

分子的光反应很大程度上取决于激发态的性质。研究激发态的波函数特性与光反应之间的关系是有趣的，因为这样的研究阐明了电子的微观运动对所产生的光反应的影响。本计画的目的是以发射光谱为主要工具，研究光化学反应的电子态依赖性。为了进行这项研究，我们做了一个发射分光光度计。我们购买了检测侧的光谱仪，检测器和控制器。在此之前，我们已经购买了激发侧的光谱仪和灯。新分光光度计的灵敏度比原分光光度计大得多，大大提高了研究效率。我们观察到水杨醛相关分子的第一和第二激发单重态的荧光，并讨论了质子转移反应的电子态依赖性。从理论上研究了波函数的节点对有机分子光反应的影响。此外，我们还研究了水杨醛相关分子在三重态和离子态的质子转移反应，2-（2 '-羟基苯基）苯并噻唑，2-（2 ′-羟基苯基）苯并恶唑和2，2 ′-联吡啶-3，3 ′-二醇，溶剂对类胡萝卜素弛豫过程的影响显示出双重发射特性，吡啶类化合物磷光弱的原因。S.长冈被选为日本化学学会的“科学无国界VII”和“第六届青年学者讲座”。他还在美国化学学会出版的《物理化学杂志》（The Journal of Physical Chemistry）上撰写了一篇特邀论文（第95卷，第100页）。10229-10235，1991）。

The photoreaction of molecules depends largely on the nature of the excited state. It is interesting to study the relationship between the characteristics of the wave function of the excited state and the photoreaction, because such a study clarifies the effect of microscopic motion of electrons on the resultant photoreaction. The purpose of this project is to study the electronic-state dependence of photoreactions mainly by means of the emission spectroscopy. In order to perform this study, we made an emission spectrophotometer. We bought the spectrometer of the detection-side, the detector, and the controller. Previously, we had already bought the spectrometer of the excitation-side and the lamp. The sensitivity of the new spectrophotometer is much larger than the old one and the efficiency of the study was enhanced very much. We observed the fluorescence from the first and second excited singlet states of the related molecules of salicylaldehyde and discussed the electronic-state dependence of the proton transfer reaction. From theoretical studies, we found the effect of the node of the wave function on the photoreaction of organic molecules. Furthermore, we studied the proton transfer reactions in the triplet state and the ionic state of the related molecules of salicylaldehyde, the proton transfer in the lowest triplet states of 2-(2'-hydroxyphenyl)benzothiazole, 2-(2'-hydroxyphenyl)benzoxazole, and 2,2'-bipyridyl-3,3'-diol, the solvent effect on the relaxation processes of carotenoids showing dual emissive characteristics, the reason for the weak phosphorescence of pyridines. S. Nagaoka was chosen as 'Kagaku No Frontier VII' and 'the 6th Young Scholar Lecture' of the Chemical Society of Japan. He also wrote an invited paper in The Journal of Physical Chemistry published from the American Chemical Society (Vol. 95, pp. 10229-10235, 1991).