Ambipolar tetrafluorodiphenylethene-based donor-acceptor copolymers: synthesis, properties, backbone conformation and fluorine-induced conformational locks
Ambipolar tetrafluorodiphenylethene-based donor-acceptor copolymers: synthesis, properties, backbone conformation and fluorine-induced conformational locks
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双极性四氟二苯乙烯基供体-受体共聚物：合成、性质、主链构象和氟诱导构象锁
DOI：
10.1039/c6py01922f
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发表时间：
2017
影响因子：
4.6
通讯作者：
Yu Gui
中科院分区：
文献类型：
--
作者：
Zhang Weifeng;Mao Zupan;Chen Zhihui;Huang Jianyao;Wei Congyuan;Gao Dong;Lin Zuzhang;Li Hao;Wang Liping;Yu Gui
在此，我们提出了三种类型的四氟二苯乙烯（TFPE）为基础的建筑块与多个F H-C和F S构象锁。在此基础上，开发了三种共聚物PD 23 TFPE、PD 26 TFPE和PD 25 TFPE。基于这些共聚物的场效应晶体管都表现出双极载流子输运特性，并且在基于PD 25 TFPE的器件中实现了最高的空穴/电子迁移率。薄膜微观结构分析表明，PD 25 TFPE形成了一个高度有序和致密的薄膜与边缘上的层状分子堆积。基于TFPE的小分子的晶体学数据表明，PD 25 TFPE呈现线性的、完全“锁定”的缀合骨架构象，而PD 23 TFPE和PD 26 TFPE具有弯曲的、完全“锁定”的或线性的、部分“锁定”的缀合骨架构象。我们的研究揭示了多构象锁的重要影响，调整骨干构象，在固态下的分子堆积模式，从而对聚合物半导体的电荷传输性能。
Herein, we present three kinds of tetrafluorodiphenylethene (TFPE)-based building blocks with multiple F⋯H–C and F⋯S conformational locks. Based on this, three copolymers PD23TFPE, PD26TFPE, and PD25TFPE were developed. Field-effect transistors based on these copolymers all exhibited ambipolar carrier transport characteristics, and the highest hole/electron mobilities were achieved in the PD25TFPE-based device. Thin film microstructure analyses suggest that PD25TFPE forms a highly ordered and dense thin film with an edge-on lamellar molecular packing. The crystallographic data of TFPE-based small molecules indicate that PD25TFPE assumes a linearly, fully “locked” conjugated backbone conformation, whereas PD23TFPE and PD26TFPE have a bent, fully “locked” or a linearly, partly “locked” conjugated backbone conformation. Our studies reveal the important influence of multiple conformation locks on tuning the backbone conformation, molecular packing mode in the solid state, and thus on the charge transport properties of polymer semiconductors.