Matsuda Megumi, Lin Chia-Yu, Sung Chih-Yuan, Lin Yan-Cheng, Chen Wen-Chang, Higashihara Tomoya
Department of Organic Materials Science, Graduate School of Organic Materials Science, Yamagata University, 4-3-16 Jonan, Yonezawa, Yamagata 992-8510, Japan.
Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan.
ACS Appl Mater Interfaces. 2023 Nov 8;15(44):51492-51506. doi: 10.1021/acsami.3c09951. Epub 2023 Oct 28.
The development of intrinsically stretchable -type semiconducting polymers has garnered much interest in recent years. In this study, three biobased dianhydrohexitol epimers of isosorbide (), isomannide (), and isoidide (), derived from cellulose, were incorporated into the backbone of a naphthalenediimide (NDI)-based -type semiconducting polymer as conjugation break spacers (CBSs). Accordingly, three polymers were synthesized through the Migita-Kosugi-Stille coupling polymerization with NDI, bithiophene, and CBSs, and the mobility-stretchability properties of these polymers were investigated and compared with those of their analogues with conventional alkyl-based CBSs. Experimental results showed that the different configurations of these epimers in CBSs sufficiently modulate the melt entropies, surface aggregation, crystallographic parameters, chain entanglements, and mobility-stretchability properties. Comparable ductility and edge-on preferred stacking were observed in polymers with - or -configurations in - and -based polymers. By contrast, with -/-configurations exhibits an excellent chain-realigning capability, a reduced crack density, and a proceeding bimodal orientation under tensile strain. Therefore, the -based polymer exhibits high orthogonal electron mobility retention of (53 and 56)% at 100% strain. This study is one of the few examples where biobased moieties are incorporated into semiconducting polymers as stress-relaxation units. Additionally, this is the first study to report on the effect of stereoisomerism of epimers on the morphology and mobility-stretchability properties of semiconducting polymers.
近年来，本征可拉伸型半导体聚合物的发展引起了广泛关注。在本研究中，从纤维素衍生而来的异山梨醇（）、异甘露糖醇（）和异艾杜糖醇（）这三种生物基二脱水己糖醇差向异构体被引入到基于萘二酰亚胺（NDI）的型半导体聚合物主链中，作为共轭断裂间隔基（CBSs）。相应地，通过与NDI、联噻吩和CBSs的Migita-Kosugi-Stille偶联聚合反应合成了三种聚合物，并对这些聚合物的迁移率-拉伸性能进行了研究，并与其具有传统烷基型CBSs的类似物进行了比较。实验结果表明，CBSs中这些差向异构体的不同构型充分调节了熔体熵、表面聚集、晶体学参数、链缠结以及迁移率-拉伸性能。在基于和的聚合物中，具有-或-构型的聚合物观察到了可比的延展性和边缘取向堆积。相比之下，具有-/-构型的表现出优异的链重排能力、降低的裂纹密度以及在拉伸应变下的双模态取向。因此，基于的聚合物在100%应变下表现出（53%和56%）的高正交电子迁移率保留率。本研究是将生物基部分作为应力松弛单元引入半导体聚合物的少数例子之一。此外，这是第一项报道差向异构体的立体异构对半导体聚合物的形态和迁移率-拉伸性能影响的研究。
