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High-quality conjugated polymers via one-pot Suzuki–Miyaura homopolymerization

机译：通过一锅Suzuki-Miyaura均聚 高质量共轭聚合物

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This paper describes a one-pot Suzuki–Miyaura homopolymerization that involves in situ borylation/cross coupling of dibrominated donor–acceptor conjugated macromonomers, in contrast to the standard Stille copolymerization of thienosilole and isoindigo monomers. Reaction kinetics investigation reveals that bis(pinacolato)diboron promotes an efficient polymerization. The homopolymer showed blue-shifted absorption compared to the Stille copolymer, which is rationalized by quantum chemical calculations of a series of oligomers containing various donor–acceptor configurations. The calculations suggest that the homopolymerization of asymmetrical macromonomers likely introduced both acceptor–acceptor and donor–donor segments into the backbone. The acceptor–acceptor segment is found to contribute mostly to the blue-shift of maximum absorption wavelength. Furthermore, detailed analysis of MALDI-TOF (matrix-assisted laser-desorption ionization-time of flight) spectra of these two polymers indicated that while the homopolymer is well defined, the Stille copolymer is end-capped mostly with the thienosilole moieties and/or methyl groups, implicating that destannylation and methyl transfer are the most-likely chain-termination pathways that limit high molecular weight. This is in sharp contrast to the homopolymerization, where chain-terminators are required to control the molecular weight for obtaining soluble material. The photovoltaic performances of bulk-heterojunction solar cells based on these polymers are compared.
机译：本文介绍了一锅Suzuki-Miyaura均聚反应，其中涉及二溴化供体-受体共轭大分子单体的原位硼酸酯化/交叉偶联，与噻吩甲硅油和异靛蓝单体的标准Stille共聚相反。反应动力学研究表明，双（频哪醇）二硼促进了有效的聚合反应。与Stille共聚物相比，该均聚物显示出蓝移的吸收，这是通过对一系列包含不同供体-受体构型的低聚物进行量子化学计算而合理化的。计算表明，不对称大分子单体的均聚可能将受体-受体链段和供体-供体链段都引入到骨架中。发现受体-受体部分主要是最大吸收波长的蓝移。此外，对这两种聚合物的MALDI-TOF（基质辅助激光解吸电离-飞行时间）光谱的详细分析表明，尽管均聚物定义明确，但Stille共聚物大多被噻吩硅烷基部分和/或噻吩甲硅烷基封端。甲基，表明脱甲锡和甲基转移是最有可能限制高分子量的链终止途径。这与均聚形成鲜明对比，后者需要链终止剂来控制分子量以获得可溶材料。比较了基于这些聚合物的体-异质结太阳能电池的光伏性能。

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