Jacob Jasmine P, Dyaga Bharath, Miralaei Mahtab, Mayarambakam Sasikumar, Boyron Olivier, Blom Paul W M, Pisula Wojciech, Schmaltz Bruno
Laboratoire de Physico-Chimie des Matériaux et des Electrolytes pour l'Energie (PCM2E), EA6299, Université de Tours, Tours, 37200, France.
Department of Molecular Physics, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, Lodz, 90-924, Poland.
Chem Asian J. 2025 Sep;20(18):e00215. doi: 10.1002/asia.202500215. Epub 2025 Jun 23.
Modifying the polymer backbone through N⋯S non-covalent interactions is an effective approach to enhance the properties of organic semiconducting polymers. Following this strategy, we designed and synthesized two new quinoidal polymers based on asymmetric and symmetric thiazole-flanked para-azaquinodimethane (p-AQM), named PAQM-TTTz and PAQM-TzTTz. To assess the impact of the thiazole unit, we also synthesized a reference polymer, PAQM-TTT, and compared its optoelectronic, thermal, and polymer backbone planarity properties with those of PAQM-TTTz and PAQM-TzTTz. Both PAQM-TTTz and PAQM-TzTTz exhibited dual-band absorption in solution, indicating pre-aggregation due to enhanced intermolecular interactions. Both polymers exhibited a low band gap. Density functional theory (DFT) studies revealed that while the thiazole unit does not alter the bond lengths of adjacent thiophenes, but it reduces torsional disorder by forming N⋯S non-covalent interactions with adjacent thiophenes in PAQM-TTTz and PAQM-TzTTz. However, due to the reduced electron richness of the conjugated backbone, a lower charge carrier mobility was observed in field-effect transistors for PAQM-TTTz and PAQM-TzTTz in comparison to PAQM-TTT. Our results highlighted the interest of non-covalent interactions in quinoidal polymers and present an alternative design strategy to control the properties of p-AQM-based quinoidal semiconducting polymers.
通过N⋯S非共价相互作用修饰聚合物主链是增强有机半导体聚合物性能的有效方法。遵循这一策略，我们设计并合成了两种基于不对称和对称噻唑侧链对氮杂醌二甲烷（p-AQM）的新型醌型聚合物，命名为PAQM-TTTz和PAQM-TzTTz。为了评估噻唑单元的影响，我们还合成了一种参考聚合物PAQM-TTT，并将其光电、热和聚合物主链平面性与PAQM-TTTz和PAQM-TzTTz的性能进行了比较。PAQM-TTTz和PAQM-TzTTz在溶液中均表现出双波段吸收，表明由于分子间相互作用增强而发生了预聚集。两种聚合物均表现出低带隙。密度泛函理论（DFT）研究表明，虽然噻唑单元不会改变相邻噻吩的键长，但它通过在PAQM-TTTz和PAQM-TzTTz中与相邻噻吩形成N⋯S非共价相互作用来减少扭转无序。然而，由于共轭主链的电子丰富度降低，与PAQM-TTT相比，PAQM-TTTz和PAQM-TzTTz在场效应晶体管中观察到较低的电荷载流子迁移率。我们的结果突出了醌型聚合物中非共价相互作用的重要性，并提出了一种控制基于p-AQM的醌型半导体聚合物性能的替代设计策略。
