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<p>Direct arylation polymerization (DArP) offers a streamlined alternative to Stille coupling for synthesizing π-conjugated donor–acceptor (DA) polymers by forming C–C bonds through formal C–H/C–X coupling, eliminating the need for toxic organotin reagents. Early DArP systems often failed to achieve both high molecular weight and low defect levels because of insufficient catalyst efficiency and selectivity. This Focus Review summarizes the development of highly efficient and selective palladium catalysts supported by the hemilabile phosphine P(2-MeOC<sub>6</sub>H<sub>4</sub>)<sub>3</sub> (<b>L1</b>). <b>L1</b> is used alone or with the coligands <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′‑tetramethylethylenediamine (TMEDA) or 2‑dicyclohexylphosphino‑2′,4′,6′‑triisopropylbiphenyl (XPhos). <b>L1</b> maintains reactive mononuclear Pd species for efficient C–H activation; TMEDA suppresses side reactions such as homocoupling and branching; and XPhos facilitates the oxidative addition of less reactive C–X bonds. These ligand systems enable high-molecular-weight polymers (number-average molecular weight up to 347,700, yields up to 100%) with well-defined structures (cross-coupling selectivity as high as &gt;99%) across a broad monomer scope. Devices based on these materials deliver up to 9.9% power conversion efficiency in organic photovoltaics and hole mobilities ≥0.3 cm<sup>2</sup>·V<sup>–1</sup>·s<sup>–1</sup> in organic thin-film transistors, comparable to those from Stille coupling. These advances firmly position DArP as a practical, tin-free platform for the precise synthesis of high-performance π-conjugated DA polymers.</p>

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Development of highly efficient and selective catalysts for direct arylation polymerization (DArP)

  • 期刊论文

  • 发表日期：

    2025年10月20日

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  • Masayuki Wakioka

摘要

Direct arylation polymerization (DArP) offers a streamlined alternative to Stille coupling for synthesizing π-conjugated donor–acceptor (DA) polymers by forming C–C bonds through formal C–H/C–X coupling, eliminating the need for toxic organotin reagents. Early DArP systems often failed to achieve both high molecular weight and low defect levels because of insufficient catalyst efficiency and selectivity. This Focus Review summarizes the development of highly efficient and selective palladium catalysts supported by the hemilabile phosphine P(2-MeOC6H4)3 (L1). L1 is used alone or with the coligands N,N,N′,N′‑tetramethylethylenediamine (TMEDA) or 2‑dicyclohexylphosphino‑2′,4′,6′‑triisopropylbiphenyl (XPhos). L1 maintains reactive mononuclear Pd species for efficient C–H activation; TMEDA suppresses side reactions such as homocoupling and branching; and XPhos facilitates the oxidative addition of less reactive C–X bonds. These ligand systems enable high-molecular-weight polymers (number-average molecular weight up to 347,700, yields up to 100%) with well-defined structures (cross-coupling selectivity as high as >99%) across a broad monomer scope. Devices based on these materials deliver up to 9.9% power conversion efficiency in organic photovoltaics and hole mobilities ≥0.3 cm2·V–1·s–1 in organic thin-film transistors, comparable to those from Stille coupling. These advances firmly position DArP as a practical, tin-free platform for the precise synthesis of high-performance π-conjugated DA polymers.