| N-Alkylation vs O-Alkylation: Influence on the Performance of aPolymeric Field-Effect Transistors Based on a Tetracyclic Lactam Building Block | |
| Mian Cai, Zhiyuan Zhao,Yanfang Liu, Xiao Wang, Yunqi Liu, Zhenggang Lan and Xiaobo Wan; Xiao Wang and Xiaobo Wan | |
| 2017-10-27 | |
| Source Publication | Macromolecules
 |
| Volume | 50Issue:21Pages:8497-8504 |
| Abstract | Lactam-containing conjugated molecules are important building blocks for conjugated polymers for high performance organic field-effect transistors (OFETs). The alkylation on conjugated lactam building blocks may preferably produce either O-alkylated or N-alkylated isomers, which might have different influences on the HOMO/LUMO energy levels, π−π stacking patterns and crystallinity of the corresponding polymers. However, the influence of Oalkylation and N-alkylation on the OFET performance of the resultant polymers has not been reported. Here, with an improved synthetic strategy, we prepared the N-alkylated isomer of dibenzonaphthyridinedione (DBND), a tetracyclic lactam building block that used to give O-alkylated product preferably, which gave us a chance to compare the influence of N-alkylated DBND (N-DBND) and O-alkylated DBND (O-DBND) on the OFET performance of the corresponding polymers. It was found that the polymer based on N-DBND exhibits a much higher hole mobility (0.55 cm2 V−1 s−1), almost 100 times greater than the one based on O-DBND (0.006 cm2 V−1 s−1). The reasons for such a huge difference were thoroughly investigated theoretically and experimentally. It was found that repeating unit in the polymer based on N-DBND exhibits a much higher dipole moment (1.56 D) than that based on O-DBND (0.49 D), which results in a much stronger intermolecular binding energy (−57.2 vs −30.0 kcal mol−1). Although both polymers exhibits very similar coplanarity and crystalline patterns, stronger intermolecular interaction of the polymer based on N-DBND leads to shorter π−π stacking distance (3.63 vs 3.68 Å), which results in a film with higher crystallinity and highly interconnected fibrillar domains, and accounts for its high charge carrier mobility, as evidenced by 2D-GIXD and AFM analysis. We come to the conclusion that the more polar amide bond in N-DBND is the major factor which governs the charge transport properties, which overwhelms the side-chain engineering effect that O-alkylation might bring in (the branching point of the side-chain of an O-DBND-based polymer is one more atom away from the polymer backbone and results in less steric hindrance). |
| Subtype | Article |
| DOI | 10.1021/acs.macromol.7b01575 |
| Indexed By | SCI |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.qibebt.ac.cn/handle/337004/9923 |
| Collection | 生物基及仿生高分子材料团队（过去） |
| Corresponding Author | Xiao Wang and Xiaobo Wan |
| Affiliation | CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy & Bioprocess Technology, Chinese Academy of Sciences |
| Recommended Citation GB/T 7714 | Mian Cai, Zhiyuan Zhao,Yanfang Liu, Xiao Wang, Yunqi Liu, Zhenggang Lan and Xiaobo Wan,Xiao Wang and Xiaobo Wan. N-Alkylation vs O-Alkylation: Influence on the Performance of aPolymeric Field-Effect Transistors Based on a Tetracyclic Lactam Building Block[J]. Macromolecules,2017,50(21):8497-8504. |
| APA | Mian Cai, Zhiyuan Zhao,Yanfang Liu, Xiao Wang, Yunqi Liu, Zhenggang Lan and Xiaobo Wan,&Xiao Wang and Xiaobo Wan.(2017).N-Alkylation vs O-Alkylation: Influence on the Performance of aPolymeric Field-Effect Transistors Based on a Tetracyclic Lactam Building Block.Macromolecules,50(21),8497-8504. |
| MLA | Mian Cai, Zhiyuan Zhao,Yanfang Liu, Xiao Wang, Yunqi Liu, Zhenggang Lan and Xiaobo Wan,et al."N-Alkylation vs O-Alkylation: Influence on the Performance of aPolymeric Field-Effect Transistors Based on a Tetracyclic Lactam Building Block".Macromolecules 50.21(2017):8497-8504. |
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