Yue Haoguo, Kong Lingqian, Wang Bo, Yuan Qing, Zhang Yan, Du Hongmei, Dong Yunyun, Zhao Jinsheng
Shandong Key Laboratory of Chemical Energy Storage and Novel Cell Technology, Liaocheng University, Liaocheng 252059, China.
College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, China.
Polymers (Basel). 2019 Dec 6;11(12):2023. doi: 10.3390/polym11122023.
Three soluble conjugated polymers, named BEDPP, FLDPP, and CADPP, were prepared through the Suzuki polymerized reaction, and employed benzene (BE), fluorene (FL), and carbazole (CA) as the donor units, respectively. The electron-deficient molecule 2,5-bis-(2-octyldodecyl)-3,6-bis-(5-bromo-thiophene)-pyrrole[3-c]pyrrole-1,4-diketone(DPP)was introduced and used as the acceptor unit. The properties of these three copolymers were studied by a series of detailed characterization analysis, including X-ray photoelectron spectroscopy (XPS), colorimetry, electrochemical measurements, spectroelectrochemistry, kinetics, quantitative calculation, and thermogravimetric (TG) analysis, etc. The results revealed that BEDPP displayed a blue color in the neutral state and a light brown color in the oxidized state, FLDPP exhibited a cyan color in the neutral state and a gray color in the oxidized state, while CADPP displayed pure blue color in the neutral state and a light gray color in the oxidized state. All these polymers possess narrow optical band gaps lower than 1.80 eV and satisfactory thermal stability. The kinetic characterization showed that the optical contrasts (ΔT%) in the near-infrared region were superior to the visible region. The optical contrasts of BEDPP, FLDPP, and CADPP are 41.32%, 42.39%, and 45.95% in the near-infrared region, respectively, which made them a good application prospect in the near-infrared region. Amid the three polymers, CADPP has the highest coloration efficiency (around about 288 cm·C) and fast switching times (0.77 s in the coloring process and 0.52 s in the bleaching process) in the visible region, and the comprehensive performance of CADPP can be comparable to that of the reported D-A (Donor-Acceptor) type blue color polymers. In general, based on the good performances and the stable neutral blue color, the three polymers had profound theoretical significance for the development of electrochromic material and the completion of the RGB (Red, Green, Blue) color space.
通过铃木聚合反应制备了三种可溶性共轭聚合物，分别命名为BEDPP、FLDPP和CADPP，它们分别以苯（BE）、芴（FL）和咔唑（CA）作为供体单元。引入缺电子分子2,5-双（2-辛基十二烷基）-3,6-双（5-溴噻吩）-吡咯并[3-c]吡咯-1,4-二酮（DPP）作为受体单元。通过一系列详细的表征分析对这三种共聚物的性能进行了研究，包括X射线光电子能谱（XPS）、比色法、电化学测量、光谱电化学、动力学、定量计算和热重（TG）分析等。结果表明，BEDPP在中性状态下呈蓝色，在氧化状态下呈浅棕色；FLDPP在中性状态下呈青色，在氧化状态下呈灰色；而CADPP在中性状态下呈纯蓝色，在氧化状态下呈浅灰色。所有这些聚合物都具有低于1.80 eV的窄光学带隙和令人满意的热稳定性。动力学表征表明，近红外区域的光学对比度（ΔT%）优于可见光区域。BEDPP、FLDPP和CADPP在近红外区域的光学对比度分别为41.32%、42.39%和45.95%，这使其在近红外区域具有良好的应用前景。在这三种聚合物中，CADPP在可见光区域具有最高的着色效率（约288 cm·C）和快速切换时间（着色过程中为0.77 s，漂白过程中为0.52 s），并且CADPP的综合性能可与已报道的D-A（供体-受体）型蓝色聚合物相媲美。总体而言，基于良好的性能和稳定的中性蓝色，这三种聚合物对电致变色材料的发展以及RGB（红、绿、蓝）颜色空间的完善具有深远的理论意义。
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