噻吩-咔唑-苯衍生物的设计、 合成及电致变色性质

doi:10.7503/cjcu20170837

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (8): 1699.doi: 10.7503/cjcu20170837

噻吩-咔唑-苯衍生物的设计、合成及电致变色性质

曲星星, 戴玉玉, 李维军, 欧阳密, 张诚()

浙江工业大学化学工程学院, 能源材料及应用国家国际科技合作基地, 杭州 310014

收稿日期:2017-12-21 出版日期:2018-08-10 发布日期:2018-05-14
作者简介:联系人简介: 张诚, 男, 博士, 教授, 博士生导师, 主要从事有机光电功能材料及器件研究. E-mail: czhang@zjut.edu.cn
基金资助:
国家自然科学基金(批准号: 51673174, 51573165, 51603185)和浙江省自然科学基金重点项目(批准号: LZ17E030001)资助.

Synthesis and Electrochromic Properties of Thiophene-carbazol-benzene Derivativies^†

QU Xingxing, DAI Yuyu, LI Weijun, OUYANG Mi, ZHANG Cheng^*()

International Sci. & Tech. Cooperation Base of Energy Materials and Application,College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

Received:2017-12-21 Online:2018-08-10 Published:2018-05-14
Contact: ZHANG Cheng E-mail:czhang@zjut.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos. 51673174, 51573165, 51603185) and the Natural Science Foundation of Zhejiang Province, China(No. LZ17E030001).

摘要/Abstract

摘要：

以苯和二联苯单元为核, 分别在其1,4位和4,4'(对位)引入噻吩-咔唑单元, 设计合成了9,9'-(1,4-亚苯基)双[3,6-双(2-噻吩)]-9-氢-咔唑(BTCPh)和9,9'-[1,1'-联苯基]-4,4'-二取代基双[3,6-双(2-噻吩)]-9-氢-咔唑(BTCBPh)2种化合物; 再通过电化学聚合得到相应的交联结构聚合物, 分别为聚9,9'-(1,4-亚苯基)双[3,6-双(2-噻吩)]-9-氢-咔唑(pBTCPh)和聚9,9'-[1,1'-联苯基]-4,4'-二取代基双[3,6-双(2-噻吩)]-9-氢-咔唑(pBTCBPh)薄膜. 利用循环伏安法(CV)、多电位阶跃、紫外-可见-近红外(UV-Vis-NIR)吸收光谱和扫描电子显微镜(SEM)等手段对其进行了表征与电化学性能测试. 结果表明, 2种聚合物均表现出良好的电化学性质、相似的颜色变化、较高的光学对比度及电化学循环稳定性等优异的电致变色性质. pBTCPh聚合物薄膜比pBTCBPh表现出更快的响应速度, 这可能是由于前者具有更加均匀规整的堆积结构, 有利于变色过程中的离子嵌入与脱出所致.

关键词: 噻吩-咔唑衍生物, 电致变色, 堆积结构, 响应时间

Abstract:

The central phenyl and biphenyl groups were introduced into the N-positions of two thiophene-carbazole structures to form the desired 9,9'-(1,4-phenylene)bis[3,6-di-2-thienyl]-9H-carbazole(BTCPh) and 9,9'-[1,1'-biphenyl]-4,4'-diylbis[3,6-di-2-thienyl]-9H-carbazole(BTCBPh), respectively. The obtained BTCPh and BTCBPh were electrochemically polymerized to generate the corresponding polymers, poly 9,9'-(1,4-phenylene)bis[3,6-di-2-thienyl]-9H-carbazole(pBTCPh) and poly 9,9'-[1,1'-biphenyl]-4,4'-diylbis[3,6-di-2-thienyl]-9H-carbazole(pBTCBPh), which might possess the cross-linked structure. The polymers were investigated by different character methods, such as cyclic voltammetry, multi-current step, ultraviolet visible near infrared absorption spectrum, scanning electron microscope and so on. The results showed that both of pBTCPh and pBTCBPh polymers exhibited excellent electrochromic properties with similar color changes, high optical contrast and good electrochemical cycle stability. And pBTCPh polymer film showed the faster color switching speed than pBTCBPh, which was ascribed to the possible more uniform stack structure in pBTCPh film. The uniform stack structure was beneficial to the fast ion inserting/deserting behavior in the electrochromic process.

Key words: Thiophene-carbazole derivative, Electrochromic color, Packing structure, Response time

中图分类号:

O622
O646

TrendMD:

曲星星, 戴玉玉, 李维军, 欧阳密, 张诚. 噻吩-咔唑-苯衍生物的设计、合成及电致变色性质. 高等学校化学学报, 2018, 39(8): 1699.

QU Xingxing, DAI Yuyu, LI Weijun, OUYANG Mi, ZHANG Cheng. Synthesis and Electrochromic Properties of Thiophene-carbazol-benzene Derivativies^†. Chem. J. Chinese Universities, 2018, 39(8): 1699.

图/表 10

Scheme 1 Synthetic route of BTCPh(n=1) and BTCBPh(n=2) and possible cross-linked structure of pBTCPh(n=1) and pBTCBPh(n=2)

Fig.1 Cyclic voltammetric curves of BTCPh(a) and BTCBPh(b) in DCM/ACN(volume ratio 9:1) solution containing 0.1 mol/L TBAP at a scan rate of 100 mV/s

Fig.2 UV-Vis absorption spectra of BTCPh(a) and BTCBPh(b) in DCM solution

Fig.3 Cyclic voltammetric curves(10 cycles) for polymerization of BTCPh(A) and

Fig.4 Cyclic voltammetric curves of pBTCPh(A) and pBTCBPh(B) in monomer free acetonitrile solution containing 0.1 mol/L TBAPScan rate from 50 mV/s to 200 mV/s, insets of (A) and (B) are the curves of pBTCPh and pBTCBPh of its redox peak current value versus scan rate, respectivley.

Fig.5 UV-Vis-NIR absorbance curves of pBTPh(A) and pBTCBPh(B) polymers in applied potential of 0—1.2 VInsets are the UV-Vis absorbance curves of pBTCPh and pBTCBPh polymers upon 0 V.

Fig.6 Optical contrast of pBTCPh(A) and pBTCBPh(B) polymers films

Fig.7 Switching time monitored at 410(A), 660(B) and 1100 nm(C) in acetonitrile solution containing 0.1 mol/L TBAP between 0 and 1.2 V with residence time of 10 sa. pBTCPh; b. pBTCBPh.

Fig.8 SEM images of pBTCPh(A) and pBTCBPh(B) polymer films

Fig.9 Cycle stability of pBTCPh(A) and pBTCBPh(A) polymers films

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噻吩-咔唑-苯衍生物的设计、合成及电致变色性质

Synthesis and Electrochromic Properties of Thiophene-carbazol-benzene Derivativies^†

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噻吩-咔唑-苯衍生物的设计、 合成及电致变色性质

Synthesis and Electrochromic Properties of Thiophene-carbazol-benzene Derivativies†

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噻吩-咔唑-苯衍生物的设计、合成及电致变色性质

Synthesis and Electrochromic Properties of Thiophene-carbazol-benzene Derivativies^†