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Extended π-Electron Delocalization in Quinoid-Based Conjugated Polymers Boosts Intrachain Charge Carrier Transport

  • Tsubasa Mikie
    Tsubasa Mikie
    Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan
    Applied Chemistry Program, Graduate School of Advanced Science and Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan
  • Masahiro Hayakawa
    Masahiro Hayakawa
    Institute for Integrated Cell-Material Sciences (iCeMS), Institute for Advanced Study, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
    Department of Chemistry, Graduate School of Science, Nagoya University, Furo, Chikusa, Nagoya 464-8602, Japan
  • Kenta Okamoto
    Kenta Okamoto
    Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan
  • Keitaro Iguchi
    Keitaro Iguchi
    Applied Chemistry Program, Graduate School of Advanced Science and Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan
  • Shuhei Yashiro
    Shuhei Yashiro
    Research Center for Functional Materials, Next generation semiconductor group, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 Japan
  • Tomoyuki Koganezawa
    Tomoyuki Koganezawa
    Japan Synchrotron Radiation Research Institute, Sayo-gun, Hyogo 679-5198, Japan
  • Masatomo Sumiya
    Masatomo Sumiya
    Research Center for Functional Materials, Next generation semiconductor group, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 Japan
  • Hiroyuki Ishii
    Hiroyuki Ishii
    Department of Applied Physics, Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan
    Material Innovation Research Center (MIRC) and Department of Advanced Materials Science, Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561, Japan
  • Shigehiro Yamaguchi
    Shigehiro Yamaguchi
    Department of Chemistry, Graduate School of Science, Nagoya University, Furo, Chikusa, Nagoya 464-8602, Japan
    Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Furo, Chikusa, Nagoya 464-8601, Japan
  • Aiko Fukazawa*
    Aiko Fukazawa
    Institute for Integrated Cell-Material Sciences (iCeMS), Institute for Advanced Study, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
    *Email: [email protected]
  • , and 
  • Itaru Osaka*
    Itaru Osaka
    Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan
    Applied Chemistry Program, Graduate School of Advanced Science and Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan
    *Email: [email protected]
    More by Itaru Osaka
Cite this: Chem. Mater. 2021, 33, 21, 8183–8193
Publication Date (Web):October 21, 2021
https://doi.org/10.1021/acs.chemmater.1c02072
Copyright © 2021 American Chemical Society

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    Supporting Info (4)»

    Abstract

    Abstract Image

    Over the past two decades, the charge carrier mobility of π-conjugated polymers has vastly improved. This has been mostly achieved by increasing the π–π stacking ability of the polymers through advanced molecular design, thereby improving “interchain” charge carrier transport. However, the rational design of π-conjugated polymers for improving “intrachain” charge carrier transport along the backbone still remains a formidable challenge. Here, we show the synthesis of a new π-conjugated polymer based on a quinoidal bithiophene moiety (PSP4T), which interestingly, was found to have significantly extended π-electron delocalization along the backbone compared to its isomer (PBTD4T), although these polymers have an identical basic structure. Importantly, despite the similar π–π stacking structure, PSP4T demonstrated transistor mobilities of around 1–2.5 cm2 V–1 s–1 that are 1–2 orders of magnitude higher than that of PBTD4T. On the basis of further investigations of energetic disorder and theoretical simulations, the higher mobility in PSP4T than in PBTD4T is most likely attributed to the remarkably higher intrachain charge carrier transport, which originates in the highly extended π-electron delocalization. We believe that our study can provide new guidelines for the design of π-conjugated polymers with high intrachain charge carrier transport.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.1c02072.

    • Synthetic details; NMR spectra for the compounds; GPC data; thermal analysis; electrochemical and optical properties; X-ray analysis for the single crystals; DFT calculations; OFET, GIXD, AFM, and PDS data; and calculated band structures (PDF)

    • Crystallographic information file for BTD2T (CIF)

    • Crystallographic information file for SP2T (CIF)

    • Crystallographic information file for SP4T-C6 (CIF)

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    This article is cited by 13 publications.

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