通过Stille偶联反应合成了一种D-A-D型单体2,3-二(4'-辛氧基苯基)-5,8-二硒吩基喹喔啉(M7),通过紫外-可见光谱、傅里叶变换红外光谱、核磁共振氢谱等测试手段进行了结构表征。通过电化学聚合制备了聚(5,8-二溴-2,3-双(4'-辛氧基苯基)喹喔啉)。从聚合物薄膜的紫外-可见光谱与循环伏安图计算的光学能隙和电化学能隙分别为1.48 e V和1.45 e V。从光谱电化学结果可以看出,电压从0~1.0 V阶梯变化时,聚合物显示电致变色并且聚合物薄膜颜色由深蓝色(中性态)变成透明的浅黄色(氧化态)。聚合物薄膜在603 nm处的紫外-可见吸收峰随着电压的增加而降低,而在863 nm出现的新吸收峰强度增强。聚合物薄膜在863 nm处的光学对比度和响应时间分别为59%和1.74 s。
Two novel monomers, 10,13-bis(4-octyl-2-thienyl)-dibenzo[a,c]phenazine (OTBP) and 10,13-bis(4-octyl-2- thienyl)-dipyrido[3,2-a:2',3'-c]phenazine (OTPP), were synthesized. Electrochemical polymerization of OTPP and OTBP were carried out in acetonitrile/dichloromethane (ACN/DCM) solvent mixture containing tetra-n- butylammoniumhexafluorophosphate (TBAPF6), and electrochromic properties of POTPP and POTBP are described. Furthermore, the effects of structural difference on electronic properties of electron acceptor units, electrochemical and electrochromic properties of two resulting polymers were examined. The results showed that the OTBP was polymerized at lower potential than OTPP, and this is because OTPP contains two more N atoms in electron acceptor unit and its electron withdrawing ability is stronger than that of OTBP. The UV-Vis-NIR spectra analysis revealed that the POTPP film has three absorption bands centered at 570 nm, 925 nm and 1581 nm, and the POTBP film has two absorptions at 566 nm and 1009 nm, respectively. The electrochromic properties indicated that the two polymer films exhibits reasonable optical contrasts and response time with low band gaps, defined as the onset of the absorption band at 570 nm for POTPP and the absorption band at 566 nm for POTBP, as 1.74 eV for POTPP and as 1.69 eV for POTBP.
以二(三苯基膦)二氯化钯[Pd(PPh3)2Cl2]或醋酸钯[Pd(OAc)2]与三环己基膦作为催化剂,通过Sonagashira或Suzuki碳-碳偶联反应制备了3种含2,3-二(4'-辛氧基苯基)-5,8-二硒吩基喹喔啉单元的聚苯撑乙炔类(P1)、聚芴类(P2)和聚咔唑类(P3)π-共轭交替共聚物。经傅里叶变换红外光谱、氢核磁共振谱、紫外-可见光谱、荧光光谱、循环伏安、X射线粉末衍射、热重和凝胶渗透色谱等测试手段对其进行了表征并研究共聚物在CHCl3-CF3COOH混合溶液中的酸致变色行为。结果表明,得到的共聚物在甲苯、氯仿、四氢呋喃等有机溶剂里具有很好的溶解性,3种共聚物在CHCl3和薄膜状态下长波长处的紫外-可见最大吸收波长分别在546 nm、542 nm、538 nm和586 nm、552 nm、558 nm处出现。共聚物的光学能隙分别为1.80 e V、1.86 e V和1.84 e V。与P1和P2相比,P3显示较好的酸致变色行为并且三氟乙酸浓度在1.346×10-3~13.46×10-3mol/L范围之间其表现出酸浓度与吸光度之间的线性关系。通过循环伏安测试,共聚物均具有一定的p掺杂和空穴传输行为。