Xiong Haigen, Lu Yu, Lin Qijie, Xie Yuke, Guo Fujun, Zhang Meng, Zhang Xin, Shi Qinqin, Huang Hui
School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering and Low-Carbon Technology, Tianjin University, Tianjin, 300072, P.R. China.
College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
Angew Chem Int Ed Engl. 2025 Aug 11;64(33):e202509672. doi: 10.1002/anie.202509672. Epub 2025 Jun 25.
The Suzuki-Miyaura cross-coupling reaction plays a pivotal role in the construction of carbon-carbon bonds, utilizing low-toxicity and readily available organoboron substrates. However, competitive protodeboronation of arylboronic acids has significantly limited its synthetic applications, particularly in the synthesis of optoelectronic polymer materials. Herein, a novel sulfonium salt-mediated Suzuki-Miyaura cross-coupling protocol is developed to synthesize high-quality π-conjugated polymers (CPs). The universality of this method was exemplified by successfully synthesizing twelve CPs with various electrophiles and nucleophiles. Impressively, the synthesized CPs exhibited enhanced optoelectronic properties, e.g., charge carrier mobilities, compared to those synthesized by traditional methods. Experimental and theoretical investigations revealed that direct transmetalation of boronic esters without prior conversion to more reactive intermediates play a critical role in this protocol, thus avoiding the problematic deboronation associated with unstable boronic acids. This method provides an environmentally benign approach to synthesize device-quality CPs.
铃木-宫浦交叉偶联反应在碳-碳键的构建中起着关键作用，它使用低毒性且易于获得的有机硼底物。然而，芳基硼酸的竞争性质子脱硼反应严重限制了其合成应用，尤其是在光电子聚合物材料的合成中。在此，开发了一种新型的锍盐介导的铃木-宫浦交叉偶联方法来合成高质量的π共轭聚合物（CPs）。通过成功合成十二种含有各种亲电试剂和亲核试剂的CPs，证明了该方法的通用性。令人印象深刻的是，与传统方法合成的CPs相比，所合成的CPs表现出增强的光电子性质，例如电荷载流子迁移率。实验和理论研究表明，硼酸酯无需预先转化为更具反应性的中间体即可直接进行转金属化反应，这在该方法中起着关键作用，从而避免了与不稳定硼酸相关的有问题的脱硼反应。该方法为合成器件级CPs提供了一种环境友好的途径。
