Synthesis of Conjugated Polymers via Direct C_H/C_Cl Coupling Reactions Using a Pd/Cu Binary Catalytic System
Synthesis of Conjugated Polymers via Direct C_H/C_Cl Coupling Reactions Using a Pd/Cu Binary Catalytic System
复制标题
使用 Pd/Cu 二元催化体系通过直接 C_H/C_Cl 偶联反应合成共轭聚合物
DOI：
10.1039/c9py00232d
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
and Takaki Kanbara
中科院分区：
文献类型：
--
作者：
Junpei Kuwabara;Wataru Tsuchida;Shuyang Guo;Ziwei Hu;Takeshi Yasuda;and Takaki Kanbara
直接芳基化缩聚被认为是合成共轭聚合物的一种有效方法。这种方法很难应用于二氯芳基单体，因为与二溴芳基单体中的C-Br键相比，C-Cl键的反应性较低，二溴芳基单体已广泛用于直接芳基化缩聚。本研究采用Pd/Cu二元催化体系，实现了二氯芳基单体的直接芳基化缩聚反应。Pd和Cu催化剂的摩尔比的优化导致以良好的产率形成高分子量聚合物。在反应机理的基础上，通过合理选择单体比例，使聚合物末端单元的结构缺陷最小化。所得聚合物具有相对低的结构缺陷，表现出较高的光致发光和电致发光的量子效率比不规则的终端结构的聚合物。
Direct arylation polycondensation is regarded as an efficient synthetic method for conjugated polymers. This methodology is difficult to apply to dichloroaryl monomers because of the low reactivity of the C–Cl bonds compared to that of the C–Br bonds in dibromoaryl monomers, which have been widely used in direct arylation polycondensation. In this research, direct arylation polycondensation of dichloroaryl monomers was achieved by the use of a Pd/Cu binary catalytic system. Optimisation of the molar ratio of the Pd and Cu catalyst resulted in the formation of high-molecular-weight polymers in good yields. Structural defects of the polymer at the terminal unit were minimised by logical choice of the monomer ratio on the basis of the reaction mechanism. The obtained polymer with relatively low structural defects showed a higher quantum efficiency of photoluminescence and electroluminescence than that of the polymer with irregular terminal structures.