Two high molecular weight conjugated polymers (CPs), i.e., poly[N,N′-bis(4-tetradecyloctadecyl)-7,7′-difluoroisoindigo-alt-2,2′-bithiazole] (P2FI2Tz) and poly[N,N′-bis(4-tetradecyloctadecyl)-5,5′,7,7′-tetrafluoroisoindigo-alt-2,2′-bithiazole] (P4FI2Tz), were synthesized via C–H/C–H oxidative direct arylation polycondensation (Oxi-DArP) using PdCl₂/CuCl/Cu(OAc)₂ as catalytic system and chlorobenzene as solvent. Both polymers are unipolar n-type semiconductors with electron mobility (μ_e) > 0.2 cm² V^–1 s^–1, attributed to their low-lying highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbital (LUMOs), which are −6.01/–3.69 and −6.24/–3.82 eV for P2FI2Tz and P4FI2Tz, respectively. P2FI2Tz was also synthesized via C–Br/C–H direct arylation polycondensation (DArP) and Stille polycondensation. The resultant polymers P2FI2Tz-D and P2FI2Tz-S showed slightly lower μ_e compared to Oxi-DArP-made polymer (P2FI2Tz-O1) with a similar molecular weight. Notably, Oxi-DArP is much faster and more efficient than DArP and Stille polycondensation. P2FI2Tz with a number-average molecular weight (M_n) above 40 kDa, was obtained in 9 h of Oxi-DArP, significantly shorter than 24 h with DArP and Stille polycondensation. P2FI2Tz with a M_n as high as 191 kDa could be synthesized via Oxi-DArP by extending the polymerization time to 16 h. Our results prove Oxi-DArP to be an efficient protocol to synthesize polymer semiconductors. This is also the first comparative study on three methods, i.e., Oxi-DArP, DArP, and Stille polycondensation.

中文翻译：

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C–H/C–H 氧化直接芳基化缩聚生成异靛蓝 n 型共轭聚合物

两种高分子量共轭聚合物（CP），即聚[ N,N'-双（4-十四烷基十八烷基）-7,7'-二氟异靛蓝-2,2'-联噻唑]（P2FI2Tz）和聚[ N , N′-双(4-十四烷基十八烷基)-5,5′,7,7′-四氟异靛蓝-2,2′-联噻唑](P4FI2Tz),通过C–H/C–H氧化直接芳基化缩聚反应合成( Oxi-DArP)以PdCl ₂ /CuCl/Cu(OAc) ₂为催化体系，氯苯为溶剂。这两种聚合物都是单极 n 型半导体，电子迁移率 (μ _e ) > 0.2 cm ² V ^–1 s ^–1，归因于它们的低位最高占据分子轨道 (HOMO) 和最低未占据分子轨道 (LUMO)， P2FI2Tz 和 P4FI2Tz 分别为 -6.01/–3.69 和 -6.24/–3.82 eV。 P2FI2Tz 还通过 C-Br/C-H 直接芳基化缩聚 (DArP) 和 Stille 缩聚合成。与具有相似分子量的 Oxi-DArP 制造的聚合物 (P2FI2Tz-O1) 相比，所得聚合物 P2FI2Tz-D 和 P2FI2Tz-S 显示出略低的 μ _e 。值得注意的是，Oxi-DArP 比 DArP 和 Stille 缩聚反应更快、更高效。 Oxi-DArP 在 9 小时内获得数均分子量 ( Mn ) 高于 40 kDa 的 P2FI2Tz，明显短于 DArP 和 Stille 缩聚反应的 24 小时_{。通过将聚合时间延长至 16 h，可以通过 Oxi-DArP 合成}M _n高达 191 kDa 的P2FI2Tz 。我们的结果证明 Oxi-DArP 是合成聚合物半导体的有效方案。这也是首次对Oxi-DArP、DArP和Stille缩聚三种方法进行比较研究。