物理化学学报 >> 2010, Vol. 26 >> Issue (12): 3310-3316.doi: 10.3866/PKU.WHXB20101201

光化学与光谱 上一篇    下一篇

基于3,4-二烷氧基噻吩的D-A-D型有机共轭分子的合成及其光学和电化学性能

祁争健, 韦斌, 王雪梅, 康凤, 洪满心, 唐兰兰, 孙岳明   

  1. 东南大学化学化工学院, 南京211189
  • 收稿日期:2010-07-15 修回日期:2010-08-24 发布日期:2010-12-01
  • 通讯作者: 祁争健, 孙岳明 E-mail:qizhengjian@seu.edu.cn, sun@seu.edu.cn
  • 基金资助:

    国家自然科学基金(21075015)和江苏省科技支撑项目(BE 2009150)资助

Synthesis, Optical and Electrochemical Properties of Novel 3,4-Dialkyloxythiophene-Based D-A-D Organic Conjugated Molecules

QI Zheng-Jian, WEI Bin, WANG Xue-Mei, KANG Feng, HONG Man-Xin, TANG Lan-Lan, SUN Yue-Ming   

  1. College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, P. R. China
  • Received:2010-07-15 Revised:2010-08-24 Published:2010-12-01
  • Contact: QI Zheng-Jian, SUN Yue-Ming E-mail:qizhengjian@seu.edu.cn, sun@seu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21075015) and Jiangsu Province Science and Technology Support Program, China (BE 2009150).

摘要:

基于Wittig 反应合成了新型D-A-D 型有机半导体材料——双(2-乙烯基-3,4-二烷氧基噻吩)-对-2,5-二苯基-1,3,4-噁二唑[(3,4DAOTV)2-OXD], 用核磁共振氢谱(1H NMR)、傅里叶变换红外(FTIR)光谱、高效液相色谱(HPLC)和元素分析法(EA)对化合物的结构进行分析和表征. 用紫外-可见(UV-Vis)光谱、荧光(PL)光谱及电化学分析研究其光学和电化学性能. 在氯仿溶液中, 各化合物的紫外最大吸收波长(λabsmax)在382-383 nm之间,光学带能隙在2.92-2.97 eV之间, 荧光最大发射波长在448-452 nm之间, 发出明亮的青色光, 荧光量子产率可达36.8%-37.6%; 在固体薄膜状态下, 各化合物于513-516 nm处发射出亮蓝绿色光. 循环伏安法研究显示: 三种大π共轭分子在正、负向区域均表现出明显的氧化、还原现象. 其中, 5.65-5.70 eV的电离势(Ip), 与噻吩类有机半导体材料的空穴传输特征相符; 电子亲和势(Ia)在2.74-2.88 eV之间, 与有机电子传输材料的特性相近, 这利于电子从阴极的注入和传输. 理论计算结果表明, 该D-A-D型共轭分子共平面性好和电荷离域程度高,对光电功能材料的分子界面组装、载流子的有效传输和器件量子效率的提高十分有利.

关键词: 光电功能材料, 烷氧基噻吩, 噁二唑, 电子供体, 电子受体

Abstract:

Novel 3,4-dialkyloxythiophene-based D-A-D organic conjugated molecules di(2-vinyl-3,4- dialkyloxythiophene)-p-2,5-bisphenyl-1,3,4-oxadiazole [(3,4DAOTV)2-OXD] were obtained using the Wittig reaction. The structure was effectively characterized using hydrogen nuclear magnetic resonance (1H NMR), Fourier transform infrared (FTIR) spectroscopy, high pressure liquid chromatography (HPLC) and elemental analysis (EA). The optical and electrochemical properties were studied by UV-Vis, fluorescence spectroscopy, and cyclic voltammetry. The UV-Vis maximum absorption of the three studied compounds ranged between 382-383 nm and their optical bandgaps ranged from 2.92 to 2.97 eV. Their emission maxima ranged from 448 to 452 nm with a bright cyan light and their luminescence quantum yields ranged from 36.8%-37.6% in CHCl3. As solid films, these compounds emit glaucous light at 513-516 nm. The (3, 4DAOTV)2-OXDs show oxidation and reduction processes in their cyclic voltammograms. Their ionization potentials of 5.65-5.70 eV coincide with the hole transport ability of thiophenes and their electron affinity values of 2.74-2.88 eV are close to the required properties of an electron transport material. These properties will facilitate electron injection and transfer from the cathode. Theoretical calculations indicate that the D-A-D organic conjugation molecule has high coplanarity and that electrons are delocalized along its backbone, which might result in interfacial molecular self-assembly and efficient charge carrier transport as well as efficient quantum yields of devices.

Key words: Functional optoelectronic material, Alkyloxypolythiophene, Oxadiazole, Donor, Acceptor

MSC2000: 

  • O649