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Oxidative (co)polymerization of dithiarubicene derivatives and electrochromic properties of narrow-bandgap conjugated polymers

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Abstract

EDOTDTR with a dithiarubicene (DTR) core and 3,4-ethylenedioxythiophene (EDOT) flanking group was synthesized by a Migita-Kosugi-Stille cross-coupling reaction. The EDOTDTR exhibited long-wavelength absorption at 822 nm and a narrow electrical bandgap energy (Egelect = 1.32 eV) due to its efficient intramolecular charge transfer. Chemical polymerization by FeCl3 in CHCl3 solution and electropolymerization on an ITO electrode yielded the conjugated polymers polyDTRchem and polyEDOTDTRelect, respectively. CV measurements revealed that the redox processes of the polymer films were reversible and not diffusion-limited. Both conjugated polymers exhibited an absorption band at 480 nm, indicating that their π-π* transitions were not much influenced by polymerization. The absorption edge of the polyEDOTDTRelect film extended into the near-infrared region (λonset > 1000 nm), implying effective intra- and intermolecular charge transfer interactions between the DTR and EDOT segments. The polyDTRchem and polyEDOTDTRelect were electrochromic active, and the corresponding color changes were brought about by applying both positive and negative potentials. In particular, both polymer films showed good switching stabilities at the oxidation potential, as confirmed by spectroelectrochemistry.

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Acknowledgements

A part of this work was financially supported by and performed under the Cooperative Research Program of “Network Joint Research Center for Materials and Devices: Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials”. The computations were performed using Research Center for Computational Science, Okazaki, Japan. KT thanks the Research Program for Next Generation Young Scientists for their support. TY is grateful to the Sakamoto Donation Foundation for financial support and to Mr. Hayashi for his kind help in setting up the experiment.

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  1. Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya, 466-8555, Japan

    Koji Takagi, Takeru Yamamori & Kenji Tsukamoto

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  1. Koji Takagi
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  2. Takeru Yamamori
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  3. Kenji Tsukamoto
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Correspondence to Koji Takagi.

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Takagi, K., Yamamori, T. & Tsukamoto, K. Oxidative (co)polymerization of dithiarubicene derivatives and electrochromic properties of narrow-bandgap conjugated polymers. Polym J 54, 1055–1062 (2022). https://doi.org/10.1038/s41428-022-00655-7

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