Photo-induced electron transfer from triplet TMB to electron poor olefins

PAN Yang; ZHAO Junshu; JI Yuanyuan; YAN Lei; YU Shuqin

您当前的位置：

首页 >

文章列表页 >

Photo-induced electron transfer from triplet TMB to electron poor olefins

Radiation Chemistry | 更新时间：2023-03-30

- Photo-induced electron transfer from triplet TMB to electron poor olefins
- Journal of Radiation Research and Radiation Processing Vol. 23, Issue 2, Pages: 82(2005)
- 作者机构：
  
  1.中国科学技术大学化学物理系　中国科学院选键化学重点实验室　合肥　230026
- 作者简介：
- 基金信息：
- DOI：
  CLC：
扫描看全文
PAN Yang, ZHAO Junshu, JI Yuanyuan, et al. Photo-induced electron transfer from triplet TMB to electron poor olefins. [J]. Journal of Radiation Research and Radiation Processing 23(2):82(2005)
DOI：

PAN Yang, ZHAO Junshu, JI Yuanyuan, et al. Photo-induced electron transfer from triplet TMB to electron poor olefins. [J]. Journal of Radiation Research and Radiation Processing 23(2):82(2005) DOI：

摘要

TMB (,N,N,N,’,N,’-四甲基联苯胺) 的气相电离能很低（6.1－6.8eV），在有机溶剂中很容易被光电离而生成阳离子自由基。此外，激发态TMB还能被氧化性强的物质氧化而失去电子。本工作利用时间分辨激光诱导瞬态吸收光谱装置,[1],，以一台Nd:YAG激光器三倍频后的355nm激光作为激发光源，详细研究了TMB和五种缺电子烯反丁烯二腈 (Fumaronitrile，FN)、反丁烯二酸二甲酯 (Dimethyl fumarate，DMF)、反丁烯二酸二乙酯 (Diethyl fumarate，DEF)、3-苯基丙烯腈 (Cinnamonitrile，CN) 和丁烯腈 (Crotononitrile，CrN)在乙腈体系中的光引发电子转移反应和动力学过程。激光脉冲后在480nm生成TMB激发三重态的特征吸收峰,[2],。加入不同缺电子烯后可以在475nm、820nm和925nm观察到归属于TMB阳离子自由基的吸收峰,[3],，相应烯烃的阴离子自由基吸收亦在不同的波段被检测到。

Abstract

Photoinduced electron transfer reactions of ,N,N,N,’,N,’- tetramethylbenzidine (TMB) with several electron poor olefins in acetonitrile solution have been studied by using laser flash photolysis and steady-state fluorescence quenching method. The triplet state of TMB at 480nm was found to undergo reductive quenching with the electron acceptors of fumaronitrile, dimethyl fumarate, cinnamonitrile, crotononitrile and diethyl fumarate. The detection of ion radical intermediates in the photolysis reactions confirms the proposed electron transfer mechanism, as expected from thermodynamics. The quenching rate constants of triplet TMB were determined at 510nm, where all the ,k,q,T, values approach or reach to diffusion controlled limit. In addition, fluorescence quenching rate constant ,k,q,S, was also obtained by calculating with Stern-Volmer equation.

关键词

瞬态吸收光谱激发三重态缺电子烯电子转移

Keywords

Transient absorption spectrumTripletElectron-poor olefinElectron transfer

references

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Pulse radiolysis of aqueous N, N-Dimethylhydroxylamine solutions

A TIME-RESOLVED STUDY ON THE PHOTODYNAMIC PRIMARY PROCESS OF ADE: II. PHOTOCHEMISTRY IN BIOMOLECULAR COMPLEXES

SPECTRAL STUDIES OF DERIVATIVE OF TRICYCLIC MODIFIED NUCLEOSIDE IN AQUEOUS SOLUTIONS

ONE-ELECTRON OXIDATION OF dGMP BY OXIDIZED RIBOFLAVIN RADICAL IN AQUEOUS SOLUTION: A LASER FLASH PHOTOLYSIS STUDY

LASER INDUCED REACTION OF ELECTRON TRANSFER FROM METHIONINE AND ITS DIPEPTIDES TO TRIPLET 4-NITROQUINOLINE 1-OXIDE

Related Author

No data

Related Institution

Institute of Radiochemistry, China Institute of Atomic Energy

Shanghai Institute of Applied Physics, Chinese Academy of Sciences

Laboratory of Radiation Chemistry, Shanghai Institute of Nuclear Research, the Chinese Academy of Science

Shanghai Institute of Materia Medica, the Chinese Academy of Science

Laboratory of Racitation Chemistry, Shanghai Institute of Nuclear Research, the Chinese Academy of Sciences

⁰