噻吩衍生物的合成及其光学性能研究  

Synthesis and optical properties of thiophene derivatives

作　　者：李林璐 刘鹏举 杨菲 郭利兵 LI Lin-lu;LIU Peng-ju;YANG Fei;GUO Li-bing(Institute of Chemistry,Henan Academy of Sciences,Zhengzhou 450002,China)

机构地区：[1]河南省科学院化学研究所有限公司,河南郑州450000

出　　处：《化学研究与应用》2023年第12期2865-2870,共6页Chemical Research and Application

基　　金：河南省科学院重大科研项目聚焦项目项目(220103001)资助。

摘　　要：以3-溴噻吩为原料,通过格氏试剂卤锂交换,在过渡金属催化下双环侨联、烷基取代,合成一种液态状双烷基-二噻吩衍生物材料,正丁基锂与三溴噻吩投料比为2:1时收率最高,达80%以上。通过紫外-可见吸收光谱和荧光光谱对其光线发射、吸收及理论计算做了系统性研究,循环伏安(CV)实验对分子内电荷转移情况进行了测试。结果表明双烷基噻吩衍生物的紫外吸收与3,3-双噻吩相比表现出较宽的光谱吸收范围优势,荧光光学能隙值及量子产率均优于3,3-双噻吩,推测衍生物中噻吩邻位增加的烷基侧链作为有效供电子基团,与主环体的Π电子体系共轭发生了明显的电子离域现象,使得双烷基噻吩衍生物具有较好的紫外-可见吸收和荧光发射响应。双烷基噻吩衍生物在不同非质子溶剂中出现随溶剂极性增大发生的吸收及发射波长红移现象,推测化合物分子与不同极性溶剂产生了相互作用,且在特定光源激发后分子内平面共轭结构产生了不同程度的偶极矩变化。最后利用伏安特性曲线验证了双烷基噻吩衍生物良好的光反应活性和导电优势,为光电材料进一步研究提供了理论基础。Using 3-bromothiophene as the raw material,a liquid dialkyl-dithiophene derivative material was synthesized by exchan-ging lithium halides with Grignard reagents,catalyzed by transition metals,and substituting alkyl groups.When the feeding ratio of N-butyllithium to tribromothiophene was 2:1,the yield could reach more than 80%.The light emission,absorption and theoretical calculations were systematically studied by Uv-Vis absorption spectroscopy and fluorescence spectroscopy,and the intramolecular charge transfer was tested by cyclic voltammetry(CV)experiments.The results showed that the ultraviolet absorption of dialkyl thio-phene derivatives exhibited a wider spectral absorption range advantage compared to 3,3-dithiophene,and the fluorescence optical energy gap value and quantum yield were beter than that of 3,3-dithiophene.It was speculated that the alkyl side chain with in-creased thiophene orthoposition in the derivative was used as an effective electron donor,and obvious electron delocalization phe-nomenon occured in the conjugation of the II electron system of the main ring,so that the dialkylthiophene derivative had a good UV-visible absorption and fluorescence emission response.Dialkylthiophene derivatives in different aprotic solvents had red shifts in absorption and emission wavelengths as the polarity of the solvent increases.The planar conjugated structures produced different de-grees of dipole moment changes.Finally,the good photoreactivity and conductive advantages of dialkylthiophene derivatives were verified by volt-ampere characteristic curves,which provided a theoretical basis for further research on optoelectronic materials.

关 键 词：双噻吩衍生物 合成 光谱吸收 伏安曲线 

分 类 号：O626[理学—有机化学]