N-Alkylation vs O-Alkylation: Influence on the Performance of a Polymeric Field-Effect Transistors Based on a Tetracyclic Lactam Building Block
文献类型：期刊论文
| 作者 | Cai, Mian1,3; Zhao, Zhiyuan2; Liu, Yanfang1; Wang, Xiao1; Liu, Yunqi2; Lan, Zhenggang1; Wan, Xiaobo1,3 |
| 刊名 | MACROMOLECULES
 |
| 出版日期 | 2017-11-14 |
| 卷号 | 50期号:21页码:8497-8504 |
| ISSN号 | 0024-9297 |
| DOI | 10.1021/acs.macromol.7b01575 |
| 英文摘要 | 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, pi-pi stacking patterns and crystallinity of the corresponding polymers. However, the influence of O-alkylation 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 cm(2) V-1 s(-1)), almost 100 times greater than the one based on O-DBND (0.006 cm2 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 pi-pi stacking distance (3.63 vs 3.68 angstrom), 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). |
| 语种 | 英语 |
| WOS记录号 | WOS:000415911100021 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/45101]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Wang, Xiao; Wan, Xiaobo |
| 作者单位 | 1.Chinese Acad Sci, CAS Key Lab Biobased Mat, Qingdao Inst Bioenergy & Bioproc Technol, 189 Songling Rd, Qingdao 266101, Peoples R China 2.Chinese Acad Sci, Inst Chem, Beijing 100080, Peoples R China 3.Univ Chinese Acad Sci, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Cai, Mian,Zhao, Zhiyuan,Liu, Yanfang,et al. N-Alkylation vs O-Alkylation: Influence on the Performance of a Polymeric Field-Effect Transistors Based on a Tetracyclic Lactam Building Block[J]. MACROMOLECULES,2017,50(21):8497-8504. |
| APA | Cai, Mian.,Zhao, Zhiyuan.,Liu, Yanfang.,Wang, Xiao.,Liu, Yunqi.,...&Wan, Xiaobo.(2017).N-Alkylation vs O-Alkylation: Influence on the Performance of a Polymeric Field-Effect Transistors Based on a Tetracyclic Lactam Building Block.MACROMOLECULES,50(21),8497-8504. |
| MLA | Cai, Mian,et al."N-Alkylation vs O-Alkylation: Influence on the Performance of a Polymeric Field-Effect Transistors Based on a Tetracyclic Lactam Building Block".MACROMOLECULES 50.21(2017):8497-8504. |
入库方式： OAI收割
来源：化学研究所
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