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Tuning of electronic properties of novel donor–acceptor polymers containing oligothiophenes with electron-withdrawing ester groups

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Abstract

To investigate the substituent effects introduced into oligothiophene units, a series of novel donor–acceptor conjugated polymers containing ester-substituted oligothiophenes were synthesized by the direct C–H arylation polycondensation of bis(ester-substituted thienyl)benzothiadiazole and dibromo-substituted oligothiophenes. The ultraviolet–visible absorption spectra of three polymers showed two absorption bands in the visible light wavelength region, ascribed to π–π* transition and the intramolecular charge transfer bands. The oxidation potentials of the polymers exhibited a negative shift with an increase in the chain length of the oligothiophene units. By comparing these polymers with alkyl-substituted analogues, it was found that the introduction of electron-withdrawing ester groups induced a negative shift in the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels and affected the LUMO rather than the HOMO energy levels. As a preliminary experiment, organic photovoltaic cells using these polymers were prepared, and their photoelectric conversion characteristics were investigated in relation to their chemical structures.

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Acknowledgements

This research was supported in part by grants from the Nakanishi Scholarship Foundation and the Murata Science Foundation (I. I.). The authors are also grateful to Dr. Tomoko Amimoto and Dr. Daisuke Kajiya, the Natural Science Center for Basic Research and Development (N-BARD), Hiroshima University for mass spectroscopy measurements, and Mr. Yoshiharu Iwai, Riken Keiki Co., Ltd., for the PESA measurement using AC–2. We would like to thank Editage (www.editage.jp) for the English language editing services.

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  1. Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Kagamiyama, Higashi-Hiroshima, Hiroshima, 739–8527, Japan

    Ichiro Imae, Naofumi Tada & Yutaka Harima

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  1. Ichiro Imae
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  2. Naofumi Tada
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Imae, I., Tada, N. & Harima, Y. Tuning of electronic properties of novel donor–acceptor polymers containing oligothiophenes with electron-withdrawing ester groups. Polym. Bull. 78, 2341–2355 (2021). https://doi.org/10.1007/s00289-020-03212-5

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