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

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    Extended π-Electron Delocalization in Quinoid-Based Conjugated Polymers Boosts Intrachain Charge Carrier Transport
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    • 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
      More by Tsubasa Mikie
      Orcidhttps://orcid.org/0000-0003-0532-8905
    • 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
      More by Masahiro Hayakawa
    • Kenta Okamoto
      Kenta Okamoto
      Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan
      More by Kenta Okamoto
    • 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
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    • 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
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    • Tomoyuki Koganezawa
      Tomoyuki Koganezawa
      Japan Synchrotron Radiation Research Institute, Sayo-gun, Hyogo 679-5198, Japan
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    • 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
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      Orcidhttps://orcid.org/0000-0003-0960-3812
    • 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
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      Orcidhttps://orcid.org/0000-0003-0644-1424
    • 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
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      Orcidhttps://orcid.org/0000-0003-0072-8969
    • 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]
      More by Aiko Fukazawa
      Orcidhttps://orcid.org/0000-0002-2903-105X
    • 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]
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      Orcidhttps://orcid.org/0000-0002-9879-2098
    Other Access OptionsSupporting Information (4)

    Chemistry of Materials

    Cite this: Chem. Mater. 2021, 33, 21, 8183–8193
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.1c02072
    Published October 21, 2021
    Copyright © 2021 American Chemical Society
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    Abstract

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    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.

    Copyright © 2021 American Chemical Society

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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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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

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    Chemistry of Materials

    Cite this: Chem. Mater. 2021, 33, 21, 8183–8193
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.1c02072
    Published October 21, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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