基于吡咯并四硫富瓦烯结构的D-π-A型化合物的合成及其非线性光学性质的理论计算  

Synthesis and Theoretical Calculation for Non-linear Properties of Pyrrolotetrathiafulvalene-Based D-π-A Diads

作　　者：安彩霞[2] 侯瑞斌[1] 邱寒[1] 赵亮[3] 尹炳柱[1] 苏忠民[3] 

机构地区：[1]长白山生物功能因子教育部重点实验室,延边大学,延吉133002 [2]河南科技学院化学化工学院,新乡 [3]东北师范大学化学学院,长春

出　　处：《应用化学》2009年第7期795-800,共6页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(20462001,20662010);教育部博士学科点科研专项基金(20060184001)资助项目

摘　　要：以吡咯并四硫富瓦烯衍生物(1)为原料,经过Vilsmeier甲酰化、Wittig反应或交叉偶联反应得到D-π-A型化合物(6a,7a),为了比较N-甲基的影响,以N-甲基吡咯并四硫富瓦烯衍生物(2)出发,用同样的方法合成了N-甲基化的D-π-A型化合物(6b,7b)。用循环伏安法(CV)和UV-Vis研究了目标化合物的电化学和光物理性质,并进行了非线性光学性质的理论计算。结果表明,目标化合物的紫外最大吸收波长在325～383nm之间,具有较长共轭结构的化合物7a和7b显示出较好的三阶非线性光学性质,它们在λ=1064nm基频下的三阶非线性系数γ值达5×10-33esu。Two tetrathiafulvalene-based D-π-A diad compounds （6a, 7a ） were prepared from starting compound（1） via Vilsmeier formylation and Wittig reaction or cross-coupling reaction. To study the effect of the N-methyl, two N-methylated D-π-A diad analogues （6b, 7b ） were also synthesized from the intermediate（2） via the same process. Their electrochemical and photophysical properties were studied with cyclic voltammetry and UV-Vis spectrometry, and theoretical calculations were carried out for their third-order nonlinear optical properties. Experimental results showed that the maximum absorption wavelengths of the target compounds were 325 - 383 nm and the results calculated showed that compounds 7a and 7b with a longer conjugated structure possessed better third-order nonliner susceptibilities, and their T values were 5 × 10^-33 esu at λ = 1 064 nm.

关 键 词：吡咯并四硫富瓦烯 电化学 光物理性质 非线性光学性质 理论计算 

分 类 号：O625.1[理学—有机化学]