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Resonance Raman spectroscopic studies of the structure of electrogenerated short-lived radicals in solution by means of column-electrolytic continuous-flow method

柱电解连续流法对溶液中电生短寿命自由基结构的共振拉曼光谱研究

基本信息

批准号：
63470029
负责人：
OKAZAKI Satoshi
金额：
$ 3.26万
依托单位：
KYOTO 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

A column-electrolytic continuous-flow method has been developed for the measurement of time-resolved resonance Raman (RR) spectra of electrogenerated short-lived organic radicals in solution. The great feature of this method is t he ease of controlling the concentration of species, which makes the method a powerful tool for the RR study of electrogenerated intermediates in solution.The RR spectrum of the thianthrenecation radical was observed and its structure in the solution was (Liscussed. based on the assignment of the RR bands. The RR spectra of the oxidezed solutions of three aromatic amines were also measured. The spectra were assigned not due to those of cation radicals but to those of dimer cation radicals produced in the consecutive reactions.The selective observation of the RR spectra of electro-generated cation radical and dication of dimethy1diphenylbenzidine were carried out by controlling the electrolysis conditions and selecting the Argon ion laser excitation lines of 488.0 and 514.0 nm. The image-intensified multi-channel photo-diode arrey detector was utilized for the acquisition of time-resolbed RR spectrum of short-lived radicals. It was proved that the time-resolution of shorter than 100 ms could be achieved in the time-resolved measurement of electro-generated species.The RR spectra of the cation radicals of anthracene derivatives and the dications of benzidine derivatives have been successfully observed by using the kripton ion laser exitation of 647.1 nm, which is infavorable conditions for the Raman measurement.

本文提出了一种柱电解连续流动法测量溶液中电生短寿命有机自由基的时间分辨共振拉曼（RR）光谱。该方法的最大特点是易于控制物种的浓度，这使得该方法成为研究溶液中电生成中间体的强有力工具。基于RR频带的分配。测定了三种芳香胺氧化溶液的RR谱。通过控制电解条件和选择488.0和514.0nm的氩离子激光激发线，选择性地观察了二甲基二苯基联苯胺电生阳离子自由基和二价阳离子的RR光谱。利用图像增强多通道光电二极管阵列探测器获得短寿命自由基的时间分辨RR谱。在647.1 nm的Kripton离子激光激发下，成功地观察到蒽衍生物阳离子自由基和联苯胺衍生物双阳离子的RR谱，为拉曼测量提供了有利条件。