KMS Qingdao Institute of Biomass Energy and Bioprocess Technology ,CAS
| N-Alkylation vs O-Alkylation: Influence on the Performance of a Polymeric Field-Effect Transistors Based on a Tetracyclic Lactam Building Block | |
Cai, Mian; Zhao, Zhiyuan; Liu, Yanfang; Wang, Xiao ; Liu; Lan, Zhenggang, Wan, Xiaobo; Wan, Xiaobo
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| 2017-12-27 | |
| Source Publication | MACROMOLECULES
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| Volume | 50Issue:21Pages:8497-8504 |
| Contribution Rank | 1 |
| 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 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 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 |
| Subject Area | Chemistry |
| WOS Headings | Polymer Science |
| DOI | 10.1021/acs.macromol.7b01575 |
| WOS Keyword | TERMINATED SIDE-CHAINS ; THIN-FILM TRANSISTORS ; CONJUGATED POLYMERS ; CHARGE-TRANSPORT ; SOLAR-CELLS ; ISOINDIGO ; ACCEPTOR ; SEMICONDUCTORS ; COPOLYMERS ; GAP |
| Indexed By | SCI |
| Language | 英语 |
| Project Number | 51573204 ; 21402220 |
| WOS Research Area | Polymer Science |
| Funding Organization | National Natural Science Foundation of China (NSFC51573204 and 21402220). |
| WOS Subject | Polymer Science |
| WOS ID | WOS:000415911100021 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.qibebt.ac.cn/handle/337004/9856 |
| Collection | 先进材料理论与模拟团队（过去） |
| Corresponding Author | Wang, Xiao; Wan, Xiaobo |
| Affiliation | CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy & Bioprocess Technology, Chinese Academy of Sciences, 189 Songling Road, Qingdao 266101, People’s Republic of China(2) Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, People’s Republic of China(3) University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of China |
| Recommended Citation 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.,...&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. |
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