Li Zijie, Shi Qinqin, Ma Xiaoying, Li Yawen, Wen Kaikai, Qin Linqing, Chen Hao, Huang Wei, Zhang Fengjiao, Lin Yuze, Marks Tobin J, Huang Hui
College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Nat Commun. 2022 Jan 10;13(1):144. doi: 10.1038/s41467-021-27832-1.
Structural defects in conjugated copolymers are severely detrimental to the optoelectronic properties and the performance of the resulting electronic devices fabricated from them. Therefore, the much-desired precision synthesis of conjugated copolymers with highly regular repeat units is important, but presents a significant challenge to synthetic materials chemists. To this end, aryl sulfides are naturally abundant substances and offer unrealized potential in cross-coupling reactions. Here we report an efficient room temperature polycondensation protocol which implements aryl disulfide C-S activation to produce defect-minimized semiconducting conjugated copolymers with broad scope and applicability. Thus, a broad series of arylstannanes and thioethers are employed via the present protocol to afford copolymers with number-average molecular weights (Ms) of 10.0-45.0 kDa. MALDI and NMR analysis of selected copolymers reveals minimal structural defects. Moreover, the polymer trap density here is smaller and the field effect mobility higher than that in the analogous polymer synthesized through thermal-activation Stille coupling.
共轭共聚物中的结构缺陷会严重损害其光电性能以及由它们制成的电子器件的性能。因此，合成具有高度规则重复单元的共轭共聚物这一备受期待的精确合成方法很重要，但对合成材料化学家来说是一项重大挑战。为此，芳基硫醚是天然丰富的物质，在交叉偶联反应中具有尚未实现的潜力。在此，我们报告了一种高效的室温缩聚方案，该方案通过芳基二硫键的C-S活化来制备具有广泛范围和适用性的缺陷最小化的半导体共轭共聚物。因此，通过本方案使用了一系列广泛的芳基锡烷和硫醚，以得到数均分子量（Mn）为10.0 - 45.0 kDa的共聚物。对选定共聚物的基质辅助激光解吸电离（MALDI）和核磁共振（NMR）分析表明结构缺陷极少。此外，此处聚合物的陷阱密度较小，场效应迁移率高于通过热活化的施蒂勒（Stille）偶联合成的类似聚合物。
