Citation: Chao Li, Zhong-yi Yuan, You-di Zhang, Chun-sheng Cai, Yu Hu, Yi-wang Chen. Semi-perfluoroalkylated Soluble Conjugated Polymers Based on Naphthalene Diimides[J]. Acta Polymerica Sinica, ;2018, 0(6): 712-720. doi: 10.11777/j.issn1000-3304.2017.17245 shu

Semi-perfluoroalkylated Soluble Conjugated Polymers Based on Naphthalene Diimides

Department of Chemistry, Nanchang University, Nanchang 330031

Corresponding author: Zhong-yi Yuan, Yi-wang Chen, yuan@ncu.edu.cn;ywchen@ncu.edu.cn
Received Date: 28 August 2017
Revised Date: 14 October 2017
Available Online: 1 March 2018

Naphthalene diimides (NDIs) as excellent organic semiconductors are difficult to be synthesized, because it is difficult to separate the key intermediate 2,6-dibromo-NDI from 2-bromo-NDI. A highly efficient synthesis of 2,6-dibromo-NDI was developed in this work. Perfluoroalkylated NDIs are excellent electron transport materials, while they are unsuitable for solution process because of their poor solubility. Since semi-perfluoroalkylated conjugated compounds have much better solubility than their perfluoroalkylated counterparts, different semi-perfluoroalkyl groups were introduced to the N-terminals of NDIs, and six conjugated polymers with donor-acceptor structure were synthesized by multi-step reactions. The chemical structure, optical properties, electrochemical properties, thermal stability, contact angle, and self-assembly properties of the target polymers were studied. The results demonstrate that suitable semi-pefluoroalkyl groups are critical to the synthesis of the soluble polymers. All these polymers are readily soluble in organic solvents. Solid absorption of these polymers red-shifts compared to their solution absorption, indicating aggregation in solid state. The absorption red-shifts obviously by increasing electron donating ability of the donor unit. The optical bandgaps of the semi-perfluoroalkylated polymers are 0.3 eV lower than those of the regular polymers. The LUMO energy levels of these polymers are as low as −3.84 ~ −3.90 eV, indicating their strong electron accepting ability. The LUMO energy levels of the semi-perfluoroalkylated polymers are about 0.1 eV lower than those of NDI polymers with regular alkyl groups, which is attributed to the strong electron-withdrawing properties of their fluorine atoms. With simple spin-coating and evaporation, the polymer P5 can be self-assembled into ordered fibers with 500 nm in length and 30 nm in width, which is in favor of charge transfer. All these polymers have good thermal stability with their decomposing temperature above 375 °C. Their higher fluorine ratio and higher contact angles are the reflection of their water repellent properties. The mobility of these polymers is measured with space charge-limiting current (SCLC) method using the device structure of ITO/ZnO/polymer/Al, and all these polymers prove to be electron transporting materials.
- Semi-perfluoroalkyl groups,
- Naphthalene diimides,
- Conjugated polymers,
- Electron transporting materials
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