N-Alkylation vs O-Alkylation: Influence on the Performance of aPolymeric Field-Effect Transistors Based on a Tetracyclic Lactam Building Block

doi:10.1021/acs.macromol.7b01575

	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
发表期刊	Macromolecules
卷号	50 期号:21 页码:8497-8504
摘要	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).
文章类型	Article
DOI	10.1021/acs.macromol.7b01575
收录类别	SCI
引用统计
文献类型	期刊论文
条目标识符	http://ir.qibebt.ac.cn/handle/337004/9923
专题	生物基及仿生高分子材料团队（过去）
通讯作者	Xiao Wang and Xiaobo Wan
作者单位	CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy & Bioprocess Technology, Chinese Academy of Sciences
推荐引用方式 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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