D-A型多色电致变色材料的电化学合成与表征
收稿日期: 2014-06-13
网络出版日期: 2014-11-07
基金资助
项目受国家自然科学基金(No.51473074)﹑中国博士后基金面上及特别资助项目(Nos.2013M530397,2014T70861)资助.
Electrosynthesis and Characterization of the Donor-Acceptor Type Multicolored Electrochromic Materials
Received date: 2014-06-13
Online published: 2014-11-07
Supported by
Project supported by the National Natural Science Foundation of China (No. 51473074), the General and Special Program of the Postdoctoral Science Foundation of China (Nos. 2013M530397, 2014T70861).
设计合成了两种新型单体, 电化学聚合制得了相应D-A型聚合物: 聚{10,13-二(3,4-乙烯二氧噻吩基)二苯并[a,c]吩嗪}(P1)和聚{10,13-二(4-乙基噻吩-2-基)二苯并[a,c]吩嗪}(P2). 研究发现, 聚合物膜P1在中性态呈现绿色, 且随着电压的增加呈现多种不同的颜色, 其在1600 nm时最大光学对比度达74.8%, 响应时间为0.6 s, 着色效率(CE)为285.8 cm2/C. 聚合物膜P2在氧化态和还原态时分别为灰蓝色和军绿色, 也具有较高的光学对比度, 快速的转换响应以及较高的着色效率. 另外, 这两种导电聚合物都具有较低的光学禁带(Eg)(P1为1.26 eV, P2为1.54 eV). 本研究提供了两种具有优良性能的电致变色材料, 并对其性能参数进行了分析研究.
关键词： 二苯并[a,c]吩嗪; 导电聚合物; D-A性能; 电化学聚合; 电致变色
侯影飞 , 徐刚强 , 赵金生 , 孔瑛 , 杨冲 . D-A型多色电致变色材料的电化学合成与表征[J]. 化学学报, 2014 , 72(12) : 1238 -1244 . DOI: 10.6023/A14060463
Two novel monomer were synthesized via Stille cross coupling reaction. Electropolymerization of the monomers gave birth to the donor-acceptor type polymers: poly{10,13-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl) dibenzo[a,c]phenazine} (P1) and poly{10,13-bis(4-ethylthiophen-2-yl)dibenzo[a,c]phenazine} (P2). Cyclic voltammetry and UV-vis spectroscopy were used to study the electrochemical and optical properties of the polymer films. The surface morphologies of the polymer films were investigated by scanning electron microscopy (SEM). The slight structural modification of the two polymer films results in the variation of the optical and electronic properties. As shown in the studies, P1 film was green in the neutral state, and with the increment of the applied potentials, four different colors were observed (light green, greyish-green, grey and cadet blue). The P1 film had prominent high optical contrast (T%) of 74.8%, excellent response time of 0.6 s and good coloration efficiency (CE) of 285.8 cm2/C at 1600 nm. Electrochromic switching response for polymer film P1 at 470 nm, 790 nm was also monitored. The slight loss in percent transmittance contrast value at the three given wavelengths indicated the stable ability of the polymer film of P1. The colors of polymer film P2 in the neutral and oxidized state were greyish-blue and cadet green, respectively. The optical contrast (T%) of P2 film was found to be 64.5%, the response time was 2.4 s and the coloration efficiency (CE) was 316.7 cm2/C at the wavelength of 1340 nm. P2 film showed high stability at the wavelength of 1340 nm, but at 754 nm the stability was not satisfactory. Moreover, both of the two polymers exhibited low optical bandgap (Eg) (the Eg of P1 was 1.26 eV and the Eg of P2 was 1.54 eV). Both polymer films revealed obvious donor-acceptor behaviors, and they were not only n-dopable but also p-dopable.
[1] Xu, N.; Shen X. D.; Cui S. Rare Metals 2010, 34, 610.
[2] Li, M.; Yang, S.-W.; Zheng, J.-M.; Xu, C.-Y. Acta Chim. Sinica 2014, 72, 456. (李梅, 杨树威, 郑建明, 徐春叶, 化学学报, 2014, 72(4), 456.)
[3] Yang, S.-W.; Zheng, J.-M.; Wu, X.-M.; Xu, C.-Y. Acta Chim. Sinica 2013, 71, 1041. (杨树威, 郑建明, 吴星明, 徐春叶, 化学学报, 2013, 71, 1041.)
[4] Jiang, Y.; Wang, J.; Guan, L.; Zhong, Y.-P.; Liu, P.; Deng, W.-J. Acta Chim. Sinica 2012, 70, 103. (姜月, 王娟, 关丽, 钟一平, 刘平, 邓文基, 化学学报, 2012, 70, 103.)
[5] Zhang, Z.-Y.; Yang, J.-P. Acta Chim. Sinica 2011, 69, 1247. (张增阳, 杨继萍, 化学学报, 2011, 69, 1247.)
[6] Amb, C. M.; Dyer, A. L.; Reynolds, J. R. Chem. Mater. 2011, 23, 397.
[7] Xu, G. Q.; Zhao, J. S.; Cui, C. S.; Hou, Y. F.; Kong, Y. Electrochim. Acta 2013, 112, 95.
[8] Sonmez, G.; Shen, C. K. F.; Rubin, Y.; Wudl, F. Angew. Chem., Int. Ed. 2004, 43, 1498.
[9] Celebi, S.; Balan, A.; Epik, B.; Baran, D.; Toppare, L. Org. Electron. 2009, 10, 631.
[10] Baran, D.; Oktem, G.; Celebi, S.; Toppare, L. Macromol. Chem. Phys. 2011, 212, 799.
[11] Özdemir, S.; Balan, A.; Baran, D.; Do?an, Ö.; Toppare, L. React. Funct. Polymer. 2011, 71, 168.
[12] Tarkuc, S.; Udum, Y. A.; Toppare, L. Thin Solid Films 2012, 520, 2960.
[13] Bulut, U.; Kolay, M.; Tarkuc, S.; Toppare, L. J. Polym. Sci., Part A: Polym. Chem. 2011, 49, 3299
[14] Cihaner, A.; Alg1, F. Adv. Funct. Mater. 2008, 18, 3583.
[15] Xu, L. Y.; Zhao, J. S.; Cui, C. S.; Liu, R. M.; Liu, J. F.; Wang, H. S. Electrochim. Acta 2011, 56, 2815.
[16] Zhu, Z. J.; Xu, J. K.; Pei, M. S.; Lu, B. Y.; Ma, C.; Li, L.; Shen, L. Acta Chim. Sinica 2010, 68, 564. (朱召进, 徐景坤, 裴梅山, 卢宝阳, 马茶, 李龙, 申亮, 化学学报, 2010, 68, 564.)
[17] Melek, P.; Tirkes, S.; Cihaner, A.; Alg1, F. Polymer 2010, 51, 62.
[18] Xu, C. X.; Zhao, J. S.; Wang, M.; Cui, C. S.; Liu, R. M. Thin Solid Films 2013, 527, 232.
[19] Kaim, W.; Fiedler, J. Chem. Soc. Rev. 2009, 38, 3373.
[20] Akp1nar, H.; Balan, A.; Baran, D.; Ünver, E. K.; Toppare, L. Polymer 2010, 51, 6123.
[21] Hu, B.; Lv, X. J.; Sun, J. W.; Bian, G. F.; Ouyang, M.; Fu, Z. Y.; Wang, P. J.; Zhang, C. Org. Electron. 2013, 14, 1521.
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