The asymmetric structure could improve the electronic properties of molecules through changing the molecular packing style. In this paper, a conjugated molecule EDOT-BE-1F (5,5′-(2-fluoro-5-(hexyloxy)-1,4-phenylene)bis(2,3-dihydrothieno[3,4–b] [1,4]dioxine)) was constructed based on the asymmetric chains (hexoxyl group and fluorine atom) para-substituted para-phenylene, and polymerized to poly(EDOT-BE-1F) by electrochemical method. The asymmetric chains endow molecule possess compromised configuration, making poly(EDOT-BE-1F) display different film morphology, hydrophobic property and molecular aggregation from symmetric polymers. The electrochromic result demonstrate that the asymmetric poly(EDOT-BE-1F) could achieve color change between red and blue with the fast respond time (0.9 s) and high coloration efficiency (305C⁻¹ cm²). Through the comparison of asymmetric poly(EDOT-BE-1F) and symmetric poly(EDOT-BE-O), we found the decreased molecular aggregation has positive influence on respond speed and coloration efficiency of polymer during reduction process, however, displays no obvious help on that of polymer during oxidation process. The relationship between molecular aggregation and electrochromic properties of conjugated polymer is discussed in detail. The result prove that the asymmetric chains could effectively modify the molecular aggregation and balance the charge transport and ion migration, which provide a simple method to modify the performance of polymer.

不对称结构可以通过改变分子堆积方式来改善分子的电子性质。在本文中，共轭分子 EDOT-BE-1 F (5,5'-(2-fluoro-5-(hexyloxy)-1,4-phenylene)bis(2,3-dihydrothieno[3,4-b]) [1,4]二恶英))是以不对称链（己氧基和氟原子）对位取代的对亚苯基为基础构建的，并通过电化学方法聚合成聚（EDOT-BE-1 F）。不对称链赋予分子具有折衷的构型，使聚 (EDOT-BE-1 F ) 显示出与对称聚合物不同的薄膜形态、疏水性和分子聚集。电致变色结果表明不对称聚（EDOT-BE-1F ) 可以实现红色和蓝色之间的颜色变化，响应时间快（0.9 s），着色效率高（305C ^-1 cm ²）。通过比较不对称poly(EDOT-BE-1 F )和对称poly(EDOT-BE- O)，我们发现在还原过程中分子聚集的减少对聚合物的响应速度和着色效率有积极的影响，而在氧化过程中对聚合物的响应速度和着色效率没有明显的帮助。详细讨论了共轭聚合物分子聚集与电致变色性能之间的关系。结果证明不对称链可以有效地改变分子聚集并平衡电荷传输和离子迁移，为聚合物性能的改变提供了一种简单的方法。