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Development of Ion Radical Salts with Melting Behavior

Research Project

Project/Area Number 19K15517
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 32020:Functional solid state chemistry-related
Research InstitutionHokkaido University

Principal Investigator

Takahashi Kiyonori  北海道大学, 電子科学研究所, 助教 (90812595)

Project Period (FY) 2019-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2020: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2019: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywordsイオンラジカル塩 / 分子性半導体・導体 / 超分子 / 相転移 / イオン伝導 / 超分子化学 / 分子性半導体 / ガラス転移
Outline of Research at the Start

イオンラジカル塩は極めて優れた電子機能を持つ一方、結晶はほとんどの溶媒に溶解せず、また加熱により融点を示さずに分解する。そのためイオンラジカル塩は、融解・溶液等の液相を経由する薄膜化やインクジェット印刷等、「ハイスループットでのデバイス製造プロセス」に適用できない。そこで、イオンラジカル塩に大環状クラウンエーテルを第3の成分として加え、融点と安定な液相を持つイオンラジカル分子導体・半導体を開発する。またイオンラジカルと組み合わせる分子を設計し、融点の制御を行う。さらに融解後の冷却で期待されるガラス相や液晶相などの中間相および相境界近傍での物性を精査し、融解するイオンラジカル塩の機能を開拓する。

Outline of Final Research Achievements

For obtaining an ionic radical salt with melting behavior, salts were prepared by combining a supramolecular cation having a flexible structure and an anion radical exhibiting electron conductivity. The structure and physical properties were evaluated to obtained salts. From systematic material synthesis, by combining a nickel dithiolate anion and a supramolecular cation consisting of an N-alkylated heteroaromatic cation and a macrocyclic crown ether, the salts exhibited a melting point. Melting point can be controlled by selecting the cation unit. The salts showed semiconducting electron conduction in the solid phase and ionic conductivity in liquid phase.

Academic Significance and Societal Importance of the Research Achievements

有機エレクトロニクス材料は「軽くて柔軟」「構造・物性の高い設計性」「比較的小さな外部刺激による電子伝導の制御性」といった優れた特長を持つため、フレキシブルデバイス、高効率エネルギー変換デバイス、大面積表示素子など、次世代電子デバイスの創製に不可欠なものと認識されている。一方、分子性イオンラジカル塩は、極めて優れた機能性の結晶が見いだされているが、電子デバイスへの応用展開はほとんど試みられていない。イオンラジカル塩が有機溶媒への難溶解性、融点を示さず分解する性質を持つためである。本研究では、イオンラジカル塩を融解させる手法を見出し、電子材料へとつなげる端緒を切り開いた。

Report

(3 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • Research Products

    (15 results)

All 2021 2020 2019

All Journal Article (5 results) (of which Peer Reviewed: 5 results,  Open Access: 3 results) Presentation (10 results) (of which Int'l Joint Research: 1 results)

  • [Journal Article] Molecular motion of halogenated ethylammonium/[18]crown-6 supramolecular ions in nickel dithiolate magnetic crystals2021

    • Author(s)
      Hasuo Naohiro、Takahashi Kiyonori、Hisaki Ichiro、Kokado Kenta、Nakamura Takayoshi
    • Journal Title

      CrystEngComm

      Volume: in press Issue: 14 Pages: 2756-2763

    • DOI

      10.1039/d1ce00253h

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] One-dimensional DABCO hydrogen-bonding chain in a hexagonal channel of magnetic [Ni(dmit)2]2020

    • Author(s)
      Li Simin、Takahashi Kiyonori、Hisaki Ichiro、Kokado Kenta、Nakamura Takayoshi
    • Journal Title

      Dalton Transactions

      Volume: 49 Issue: 46 Pages: 16772-16777

    • DOI

      10.1039/d0dt03386c

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Crystal structure and thermoresponsive luminescence of a 9,10-bis(phenylethynyl)anthracene-based cyclophane2020

    • Author(s)
      Yoshimitsu Sagara, Kiyonori Takahashi,Takayoshi Nakamura, Nobuyuki Tamaoki
    • Journal Title

      Molecular Systems Design & Engineering

      Volume: 1 Issue: 1 Pages: 205-211

    • DOI

      10.1039/c9me00105k

    • NAID

      120006950868

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Mechanochromic Luminescence from Crystals Consisting of Intermolecular Hydrogen‐Bonded Sheets2019

    • Author(s)
      Yoshimitsu Sagara, Kiyonori Takahashi,Takayoshi Nakamura, Nobuyuki Tamaoki
    • Journal Title

      Chemistry - An Asian Journal

      Volume: 15 Issue: 4 Pages: 478-482

    • DOI

      10.1002/asia.201901679

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Hydrogen‐Bonded Polyrotaxane Cation Structure in Nickel Dithiolate Anion Radical Salts: Ferromagnetic and Semiconducting Behavior Associated with Structural Phase Transition2019

    • Author(s)
      Shirakawa Yuki、Takahashi Kiyonori、Sato Hiroyasu、Hoshino Norihisa、Anetai Hayato、Noro Shin‐ichiro、Akutagawa Tomoyuki、Nakamura Takayoshi
    • Journal Title

      Chemistry A European Journal

      Volume: - Issue: 28 Pages: 6920-6927

    • DOI

      10.1002/chem.201806230

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] Magnetism of Nickel Dithiolate Crystal with Rotating Pyridazinium Cation in Supramolecular Dibenzo[24]crown-8 Columnar Structure2021

    • Author(s)
      Kiyonori Takahashi, Yuki Shirakawa, Takayoshi Nakamura
    • Organizer
      The 1st Asian Conference on Molecular Magnetism
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] pyridinium誘導体/crown ether超分子カチオンを導入した[Ni(dmit)2]塩の構造と熱挙動2020

    • Author(s)
      高橋 仁徳、土井雄登、星野 哲久、久木 一朗、芥川 智行、中村 貴義
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Crystalline polymorphism and reversible H2O sorption behavior of [Ni(dmit)2] salt with supramolecular cation unit with multiple hydrogen-bonding sites2020

    • Author(s)
      Simin Li、Kiyonori Takahashi、Jiabing Wu、Ichiro Hisaki、Takayoshi. Nakamura
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] ピリジニウム誘導体とクラウンエーテルを含む[Ni(dmit)2]アニオンラジカル塩の構造と物性2020

    • Author(s)
      土井 雄登、白川 祐基、高橋 仁徳、久木 一朗、中村 貴義
    • Organizer
      化学系学協会北海道支部2020年冬季研究発表会
    • Related Report
      2019 Research-status Report
  • [Presentation] Structures and Physical Properties of a new class of supramolecular crystals (x-aminopyridinium) (DB[24]crown8)[Ni(dmit)2](x = 2 3 4)2019

    • Author(s)
      Simin Li、Jiabing Wu、Kiyonori Takahashi、Ichiro Hisaki、Takayoshi Nakamura
    • Organizer
      the 7th Asian Conference on Coordination Chemistry(ACCC7)
    • Related Report
      2019 Research-status Report
  • [Presentation] Crystal Polymorphs and Physical Properties of (4-aminopyridinium)(dibenzo[24]crown-8)[Ni(dmit)2]-2019

    • Author(s)
      Simin Li、Kiyonori Takahashi、Jiabing Wu、Ichiro Hisaki、Takayoshi Nakamura
    • Organizer
      The 20th RIES-HOKUDAI International Symposium
    • Related Report
      2019 Research-status Report
  • [Presentation] Switch of Conductive Mechanism by Melting Behavior of Semiconducting Anion Radical Salts2019

    • Author(s)
      Kiyonori Takahashi、Yuki Shirakawa、Norihisa Hoshino、Ichiro Hisaki、Tomoyuki Akutagawa、Takayoshi Nakamura
    • Organizer
      The 20th RIES-HOKUDAI International Symposium
    • Related Report
      2019 Research-status Report
  • [Presentation] Phase Transition Behavior of Anion Radical Salts with Supramolecular Cation Structure2019

    • Author(s)
      Kiyonori Takahashi、Yuki Shirakawa、Norihisa Hoshino、Ichiro Hisaki、Tomoyuki Akutagawa、Takayoshi Nakamura
    • Organizer
      The Seventh International Symposium on the New Frontiers of Thermal Studies of Materials
    • Related Report
      2019 Research-status Report
  • [Presentation] Melting Behavior of Semiconducting Anion Radical Salts with Supramolecular Cation2019

    • Author(s)
      Kiyonori Takahashi、Yuki Shirakawa、Norihisa Hoshino、Ichiro Hisaki、Tomoyuki Akutagawa、Takayoshi Nakamura
    • Organizer
      The 2nd edition of the International Symposium of CEFMS-NCTU RCAS-AS (Taiwan) and 5-star Alliance
    • Related Report
      2019 Research-status Report
  • [Presentation] Supramolecular structure and physical properties of [Ni(dmit)2] salts with dibenzo-24-crown-82019

    • Author(s)
      Kiyonori Takahashi、Ichro Hisaki、Yuki Shirakawa、Takayoshi Nakamura
    • Organizer
      The 9th International conference on Organic Electronics (ORGEL-2019)
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2022-01-27  

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