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Effect of substituents on self-assembling behaviors and charge transport properties of nonplanar heterocycloarenes

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Abstract

(Hetero)cycloarenes possessing rigid molecular skeletons and large π-systems are the potential active materials in various electronic devices. However, the development of their organic electronics still lags far behind the synthetic chemistry. Herein, in order to bridge this gap, we reported the study of organic semiconductor materials based on heterocycloarenes in detail about the relationship between structure, properties, and device performance. Three varying straight alkyl chain substituted butterfly-shaped heterocycloarenes PTZs were strategically synthesized. Compared with bulky aryl(mesityl) substituted PTZ1, PTZs show additional self-assembly behavior. Concentration-dependent 1H NMR spectra indicated that the self-assembly behavior can be modulated by the alkyl chain length. Medium alkyl chain length substituted heterocycloarene PTZ-C6 showed the strongest association constants of 490 M−1 in solution, and a similar trend was also observed in solid state by thin film absorption spectra. Remarkably, despite the nonplanar conjugated backbones, solution-processing thin film transistor based on PTZ-C6 exhibits hole mobility up to 0.13 cm2 V−1 s−1 and considerable current on/off ratio of 105. Our study demonstrates that substituent engineering of heterocycloarenes is a powerful strategy for modulating self-assembling structures and promoting transistor device performance.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (52073063, 61890940), the National Key R&D Program of China (2018YFA0703200), the Natural Science Foundation of Shanghai (22ZR1405800 and 23ZR1405100), the Program for Professor of Special Appointment (Eastern Scholar) at the Shanghai Institutions of Higher Learning.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Materials Science, State Key Laboratory of Molecular Engineering of Polymers, Fudan University, Shanghai, 200433, China

    Jiangyu Zhu, Wenhao Li, Rong Zhang, Yan Zhao, Xuefeng Lu & Yunqi Liu

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  1. Jiangyu Zhu
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  2. Wenhao Li
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  3. Rong Zhang
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  4. Yan Zhao
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  5. Xuefeng Lu
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Correspondence to Yan Zhao, Xuefeng Lu or Yunqi Liu.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Zhu, J., Li, W., Zhang, R. et al. Effect of substituents on self-assembling behaviors and charge transport properties of nonplanar heterocycloarenes. Sci. China Chem. 66, 2903–2911 (2023). https://doi.org/10.1007/s11426-023-1743-4

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  • DOI: https://doi.org/10.1007/s11426-023-1743-4

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