Aqueous palladium-catalyzed direct arylation polymerization (DArP) of 2-bromothiophene derivatives 6-(2-(2-bromothiophen-3-yl)ethoxy)hexyl trimethylammonium bromide (T1) and 4-(2-(2-bromothien-3-yl)ethoxy)butylsulfonate (T2) is achieved. The supporting ligand, triphenylphosphine-3,3',3''-trisulfonic acid trisodium salt (m-TPPTs), facilitates DArP of both derivatives; however, its separation from the polymers by dialysis is difficult due to its strong aggregation in water and N,N-dimethylacetamide (DMAc). This is supported by dynamic light scattering, gel permeation chromatography (GPC), and single-crystal X-ray crystallography. Pyrimidine-Pd(OAc)2 is utilized in the DArP of T1 to afford PT1 without ligand contamination. Density functional theory calculations to determine the coordinating capability of the carboxylate/pivalic acid/water to palladium indicate the viability of implementing DArP in water. Finally, polyelectrolyte molecular-weight overestimation by GPC in water is attributed to the polyelectrolyte effect. Aggregation of the conjugated polyelectrolytes leads to a contracted hydrodynamic volume, and the molecular weight and dispersity assessed by GPC in DMAc significantly deviate from the actual values. An objective approach to evaluate the molecular weight for conjugated polyelectrolytes requires further development.

中文翻译：

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2-溴噻吩衍生物的水钯催化的直接芳基化聚合。

2-溴噻吩衍生物6-（2-（2-溴噻吩-3-基）乙氧基）己基三甲基溴化铵（T1）和4-（2-（2-溴噻吩-3-）的钯水溶液催化芳基化聚合（DArP）获得了乙）乙氧基）丁基磺酸盐（T2）。支撑配体三苯基膦-3,3'，3''-三磺酸三钠盐（m-TPPTs）促进两种衍生物的DArP; 然而，由于其在水中和N，N-二甲基乙酰胺（DMAc）中的强聚集性，难以通过透析将其与聚合物分离。动态光散射，凝胶渗透色谱（GPC）和单晶X射线晶体学对此提供了支持。嘧啶-Pd（OAc）2用于T1的DArP中，可提供不受配体污染的PT1。确定羧酸盐/新戊酸/水与钯的配位能力的密度泛函理论计算表明了在水中实​​施DArP的可行性。最后，水中GPC对聚电解质分子量的高估归因于聚电解质效应。共轭聚电解质的聚集导致收缩的流体力学体积，并且通过GPC在DMAc中评估的分子量和分散性显着偏离实际值。评估共轭聚电解质分子量的客观方法需要进一步发展。共轭聚电解质的聚集导致收缩的流体力学体积，并且通过GPC在DMAc中评估的分子量和分散性显着偏离实际值。评估共轭聚电解质分子量的客观方法需要进一步发展。共轭聚电解质的聚集导致收缩的流体力学体积，并且通过GPC在DMAc中评估的分子量和分散性显着偏离实际值。评估共轭聚电解质分子量的客观方法需要进一步发展。