Structure-Function Relationships of High-Electron Mobility Naphthalene Diimide Copolymers Prepared Via Direct Arylation
Structure-Function Relationships of High-Electron Mobility Naphthalene Diimide Copolymers Prepared Via Direct Arylation
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DOI：
10.1021/cm503033j
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发表时间：
2014-11-11
影响因子：
8.6
通讯作者：
Sommer, Michael
中科院分区：
文献类型：
--
作者：
Luzio, Alessandro;Fazzi, Daniele;Sommer, Michael
直接芳基化（DA）是一种非常有前途的方法，可以从简单和环境友好的构建块构建用于大面积电子学的廉价共轭材料。在这里，我们表明，排他性的α-CH选择性是可行的，在DA的p-延伸的单体具有未取代的噻吩或呋喃单元，导致完全线性的材料。以萘二酰亚胺（NDI）、呋喃（Fu）、噻吩（Th）和四氟苯（F-4）为单体，合成了两种新的萘二酰亚胺基共轭共聚物P（FuNDIFuF（4））和P（ThNDIThF 4）。深入了解structurefunction关系是由密度泛函理论（DFT）计算和各种实验技术，从而杂原子的光学，结构和电子性质的影响进行了研究。呋喃（Fu）的使用允许增强的溶解度、由于Fu的较小尺寸而导致的NDI和Fu之间的较小二面角、以及固态下的较小pp堆叠距离。与P（ThNDIThF 4）相比，P（FuNDIFuF 4）也表现出更多的边缘取向。尽管P（FuNDIFuF（4））具有这些有利的性质，但P（ThNDIFuF 4）表现出最高的电子迁移率：类似于1.3 cm（2）/（Vs），这是P（FuNDIFuF（4））的大约3倍。P（ThNDIThF 4）的增强的OFET性能通过减少取向无序和形成梯田状薄膜形态来解释。
Direct arylation (DA) is emerging as a highly promising method to construct inexpensive conjugated materials for large-area electronics from simple and environmentally benign building blocks. Here, we show that exclusive a-CH selectivity is feasible in the DA of p-extended monomers having unsubstituted thiophene or furan units, leading to fully linear materials. Two new naphthalene diimide-based conjugated copolymersP(FuNDIFuF(4)) and P(ThNDIThF4), composed of naphthalene diimide (NDI), furan (Fu) or thiophene (Th), and tetrafluorobenzene (F-4)are synthesized. Insight into structurefunction relationships is given by density functional theory (DFT) calculations and variety of experimental techniques, whereby the effect of the heteroatom on the optical, structural, and electronic properties is investigated. The use of furan (Fu) allows for enhanced solubilities, a smaller dihedral angle between NDI and Fu as a result of the smaller size of Fu, and a smaller pp-stacking distance in the solid state. P(FuNDIFuF4) also exhibits a more edge-on orientation compared to P(ThNDIThF4). Despite these advantageous properties of P(FuNDIFuF(4)), P(ThNDIThF4) exhibits the highest electron mobility: similar to 1.3 cm(2)/(V s), which is a factor of similar to 3 greater than that of P(FuNDIFuF(4)). The enhanced OFET performance of P(ThNDIThF4) is explained by reduced orientational disorder and the formation of a terrace-like thin-film morphology.