Direct arylation polymerization (DArP) has gained interest in materials chemistry as a method to synthesize conjugated polymers with minimal use of harsh reagents and additional steps. Traditional DArP conditions do not readily yield ideal polymerization characteristics, including chain-growth and low dispersities. It would be of great utility to advance DArP methodology to become competitive with traditional conjugated polymerization techniques. We have developed conditions for a dual-catalytic Ag–Pd system for the synthesis of poly(3-hexylthiophene) (P3HT) that exhibits chain-growth kinetics, low dispersities, and catalyst chain association by Pd. Specifically, the presence of Ag-carboxylate additives plays a beneficial role in the polymerization as a C–H activating agent, while PEPPSI-iPr is used as the Pd source for C–C coupling. The addition of pyridine is necessary to inhibit Pd-mediated C–H activation in the interest of catalyst orthogonality, which can lower dispersities.

中文翻译：

---

双催化Ag-Pd体系直接芳基化聚合合成聚(3-己基噻吩)

直接芳基化聚合 (DArP) 作为一种合成共轭聚合物的方法，在材料化学中引起了人们的兴趣，该方法使用最少的刺激性试剂和额外的步骤。传统的 DArP 条件不容易产生理想的聚合特性，包括链增长和低分散性。推进 DArP 方法以与传统的共轭聚合技术竞争将是非常有用的。我们已经开发了用于合成聚 (3-己基噻吩) (P3HT) 的双催化 Ag-Pd 系统的条件，该系统表现出链增长动力学、低分散性和 Pd 的催化剂链缔合。具体来说，Ag-羧酸盐添加剂的存在作为 C-H 活化剂在聚合中发挥了有益作用，而 PEPPSI-iPr 用作 C-C 偶联的 Pd 源。