Tuning “ligandless” direct arylation polymerization toward less-branching EDOT polymers†

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry Pub Date : 2024-11-22 DOI:10.1039/d4py01212g

Xilin Pei , Quan Yang , Yanlu Sun , Wei Wu , Jianyong Yu , Yong He

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Abstract

Direct arylation polymerization conditions can be classified into phosphine-assisted and “ligandless” conditions. We compared the outcomes of five poly[thiophene-derivative-alt-EDOT]s and polymerized under two kinds of conditions. The results revealed that the “ligandless” conditions led to higher polymerization efficiency compared to phosphine-assisted conditions when employing n-hexyl functionalized EDOT as an arylative substrate and various dibromoarenes as oxidative substrates. Computational studies revealed that the phosphine-assisted conditions follow the standard concerted metalation–deprotonation (CMD). In contrast, the amide-assisted conditions follow electrophilic CMD. This mechanistic difference provides a reasonable explanation for the preference of “ligandless” conditions towards the activation of electron-donating arenes. Additionally, the use of sterically hindered amide solvents and dibromoarenes helps reduce branching defects, preserving the desired linear polymer structure.

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调整“无配体”直接芳基化聚合到少支化EDOT聚合物

直接芳基化聚合条件可分为膦辅助聚合条件和无配体聚合条件。我们比较了五种聚[噻吩衍生物-alt- edot]s和PEDOTF在两种条件下的聚合结果。结果表明，以正己基功能化EDOT为芳基底物，以各种二溴芳烃为氧化底物时，“无配体”条件下的聚合效率高于膦辅助条件。计算研究表明，磷化氢辅助条件符合标准协同金属-去质子化（CMD）。相反，酰胺辅助条件遵循亲电性CMD。这种机制上的差异为“无配体”条件对供电子芳烃活化的偏好提供了合理的解释。此外，使用位阻酰胺溶剂和二溴芳烃有助于减少分支缺陷，保持所需的线性聚合物结构。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Polymer Chemistry POLYMER SCIENCE-

CiteScore

8.60

自引率

8.70%

发文量

535

审稿时长

1.7 months

期刊介绍： Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.