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Development of Solid-State Molecular Machine Based On Pseudo-rotaxane Structure

Research Project

Project/Area Number 21K14691
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 35030:Organic functional materials-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) 2021-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2022: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2021: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Keywords超分子化学 / 分子運動 / 固相分子機械 / 擬ロタキサン / リラクサー / 強誘電体 / 分子結晶 / 分子機械 / 結晶内分子運動 / 超分子カチオン / 強誘電性 / 固相分子運動 / 超分子科学 / 分子磁性
Outline of Research at the Start

これまで多くの分子機械が構築されている一方で、それらを「機械」として動作させ外部に出力をもたらすことは極めて難しい。分子機械同士が向きの揃った高密度な運動を起こすことができれば、分子の運動を“機能”として利用可能だと予想できる。しかし結晶相での報告が少ないのは、結晶中では分子が密に詰まるため、そもそも分子が運動できる空間を確保することが難しいからに他ならない。申請者は、小さな軸状分子が環状分子を貫通した擬ロタキサンを含む結晶に着目し、小さな軸状分子が結晶内で運動可能な系の構築を考案した。得られた擬ロタキサンの結晶中で軸状分子が運動する結果として、強誘電性などの機能に結び付かないか、検討を行う。

Outline of Final Research Achievements

pseudorotaxane-type supramolecular cations were prepared as counter cation of [Ni(dmit)2] salts and their single crystal structures were investigated in correlation with their dielectric responses.
Supramolecular cation consisted of dibenzo[24]crown-8 and dialkylammonium with carbon chain lengths of 1, 3, and 4 could be prepared. In the salts with carbon chain lengths of 3 and 4, dialkylammonium was disordered at two sites, suggesting molecular motion in the crystalline state. The salt with bis(chloroethyl)ammonium showed a dielectric response similar to that of relaxor ferroelectrics.

Academic Significance and Societal Importance of the Research Achievements

リラクサー強誘電体は、結晶内でのナノ分極秩序に基づく。一次元鎖状に配列する擬ロタキサン型超分子カチオン集合体は、嵩高いdibenzo[24]crown-8 によって隣接鎖間の相互作用が無視できるほど小さいことが想定できる。すなわち、単一次元鎖の配列に基づく新奇なリラクサー強誘電性が実現している可能性がある。分子レベルでの低次元秩序に基づく強誘電性システムは類例に乏しく、新しいリラクサー強誘電体としてのポテンシャルを示すことができた。

Report

(3 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Research-status Report
  • Research Products

    (47 results)

All 2023 2022 2021

All Journal Article (7 results) (of which Peer Reviewed: 7 results,  Open Access: 3 results) Presentation (40 results) (of which Int'l Joint Research: 17 results,  Invited: 2 results)

  • [Journal Article] Multifunctional Triggering by Solid-Phase Molecular Motion: Relaxor Ferroelectricity, Modulation of Magnetic Exchange Interactions, and Enhancement of Negative Thermal Expansion2023

    • Author(s)
      Li, Simin; Takahashi, Kiyonori; Huang, Rui-Kang; Xue, Chen; Kokado, Kenta; Hoshino, Norihisa; Akutagawa, Tomoyuki; Nishihara, Sadafumi; Nakamura, Takayoshi
    • Journal Title

      Chemistry of Materials

      Volume: 35 Issue: 6 Pages: 2421-2428

    • DOI

      10.1021/acs.chemmater.2c03552

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Unique Thermal Structural Phase Transitions Exhibited by Unsymmetrical Organometallic Gold(III)‐Dithiolene Complexes with Pentylthio and Hexylthio Groups2023

    • Author(s)
      Arata Sonomi、Kim Yuna、Hoshino Norihisa、Tahara Keishiro、Takahashi Kiyonori、Kadoya Tomofumi、Inoue Tomonori、Nakamura Takayoshi、Akutagawa Tomoyuki、Yamada Jun‐ichi、Kubo Kazuya
    • Journal Title

      European Journal of Inorganic Chemistry

      Volume: 26 Issue: 12

    • DOI

      10.1002/ejic.202300017

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Uniaxial negative thermal expansion induced by molecular rotation in a one-dimensional supramolecular assembly with associated peculiar magnetic behavior2023

    • Author(s)
      Takahashi Kiyonori、Shirakawa Yuki、Sakai Hiroki、Hisaki Ichiro、Noro Shin-ichiro、Akutagawa Tomoyuki、Nakano Motohiro、Nakamura Takayoshi
    • Journal Title

      Journal of Materials Chemistry C

      Volume: 11 Issue: 5 Pages: 1891-1898

    • DOI

      10.1039/d2tc04874d

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Crystal Structure of a 4,7-Bis(phenylethynyl)-2,1,3-benzothiadiazole-Based Cyclophane and the Mechanoresponsive Luminescence2022

    • Author(s)
      Hiratsuka Keiko、Salim Fazil Thuluvanchery、Takahashi Kiyonori、Nakamura Takayoshi、Sagara Yoshimitsu
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 95 Issue: 10 Pages: 1474-1480

    • DOI

      10.1246/bcsj.20220216

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Fluoride-bridged dinuclear dysprosium complex showing single-molecule magnetic behavior: supramolecular approach to isolate magnetic molecules2022

    • Author(s)
      Wu Dong-Fang、Takahashi Kiyonori、Fujibayashi Masaru、Tsuchiya Naoto、Cosquer Goulven、Huang Rui-Kang、Xue Chen、Nishihara Sadafumi、Nakamura Takayoshi
    • Journal Title

      RSC Advances

      Volume: 12 Issue: 33 Pages: 21280-21286

    • DOI

      10.1039/d2ra04119g

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Solvent dependence of crystal structure and dielectric relaxation in ferromagnetic [MnCr(oxalate)3]- salt2022

    • Author(s)
      Wu Jia-bing、Huang Rui-Kang、Takahashi Kiyonori、Nakamura Takayoshi
    • Journal Title

      Dalton Transactions

      Volume: 51 Issue: 27 Pages: 10595-10600

    • DOI

      10.1039/d2dt01615j

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dipole fluctuation and structural phase transition in hydrogen-bonding molecular assemblies of mononuclear CuII complexes with polar fluorobenzoate ligands2021

    • Author(s)
      Takahashi Kiyonori、Miyazaki Yuji、Noro Shin-ichiro、Nakano Motohiro、Nakamura Takayoshi、Akutagawa Tomoyuki
    • Journal Title

      Dalton Transactions

      Volume: 50 Issue: 39 Pages: 13680-13685

    • DOI

      10.1039/d1dt02118d

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Presentation] 2-ハロエチルアンモニウムとベンゾ[18]クラウン-6からなる超分子カチオンを導入した[Ni(dmit)2] 塩の構造と誘電物性2023

    • Author(s)
      高橋 仁徳*,蓮尾 直洋,金丸 和矢,黄 瑞康,薛 晨,中村 貴義
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] (CH3CH2CH2)2NH2+)x((ClCH2CH2)2NH2+)1-x(dibenzo[24]crown-8) 擬ポリロタキサン超分子構造の誘電応答2023

    • Author(s)
      堀川 真実子*,高橋 仁徳,広瀬 昂生,黄 瑞康,薛 晨,中村 貴義
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] (x-fluoroanilinium)(benzo[18]crown-6)[FeCr(oxalate)3]結晶の構造と物性2023

    • Author(s)
      リュウ キヨウ*,高橋 仁徳,黄 瑞康,薛 晨,中村 貴義
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] (2,2'-Oxybis(ethylaminium))(benzo[18]crown-6)[Ni(dmit)2]結晶における分子運動と連動した熱膨張変化2023

    • Author(s)
      羽田 将人*,高橋 仁徳,黄 瑞康,薛 晨,中村 貴義
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 2-ヒドロキシ-2-メチルプロパン-1-アンモニウム/ジベンゾ[18]クラウン-6超分子カチオンを導入した[Ni(dmit)2]塩の結晶溶媒脱離にともなう構造変化と磁性2023

    • Author(s)
      金丸 和矢*,高橋 仁徳,黄 瑞康,薛 晨,中村 貴義
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 一次元的な強誘電応答を示す{((ClCH2CH2)2NH2+)(dibenzo[24]crown-8)}n超分子集合体の構築と単一次元鎖磁石とのハイブリッド化の試み2023

    • Author(s)
      京谷 悠里*,高橋 仁徳,広瀬 昂生,黄 瑞康,薛 晨,中村 貴義
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Towards molecular multiferroics by supramolecular rotors and ferromagnetic [MnCr(oxalate)3]- salts2023

    • Author(s)
      R. Huang*,J. Wu,K. Takahashi,T. Nakamura
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 超分子カチオンを導入した[Ni(dmit)2]塩における分子再配列と連動した負の熱膨張と特異な磁気特性2023

    • Author(s)
      高橋 仁徳*
    • Organizer
      分子系の複合電子機能 第 181 委員会 最終研究会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] "Unusual magnetic response associated with negative thermal expansion of [Ni(dmit)2] crystals2022

    • Author(s)
      K. Takahashi*,R. Huang,C. Xue,T. Nakamura
    • Organizer
      The 73rd Yamada Conference
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Relaxor-like dielectric response of [Ni(dmit)2] crystals containing pseudo-rotaxane supramolecular cations2022

    • Author(s)
      M. Horikawa*,K. Hirose,K. Takahashi,R. Huang,C. Xue,T. Nakamura
    • Organizer
      The 73rd Yamada Conference
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] An Attempt to Develop One-Dimensional Molecular Electret Coexisting with Low-Dimensional Magnetism Using Supramolecular Structures2022

    • Author(s)
      Y. Kyoya*,K. Hirose,K. Takahashi,R. Huang,C. Xue,T. Nakamura
    • Organizer
      The 73rd Yamada Conference
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] "Synthesis of [FeIICrIII(oxalate)3]- complexes with supramolecular cation structures2022

    • Author(s)
      X. Liu*,Z. Diao,R. Huang,K. Takahashi,C. Xue,T. Nakamura
    • Organizer
      The 73rd Yamada Conference
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Cooperative Supramolecular Motion in Magnetic Crystals for Multifunctional Materials2022

    • Author(s)
      K. Takahashi,J. Wu,S. Li,R. Huang,C. Xue,T. Nakamura*
    • Organizer
      The 14th International Symposium on Crystalline Organic Metals, Superconductors and Magnets (ISCOM2022)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Towards molecular multi-ferroelectrics by supramolecular rotor and ferromagnetic [MnCr(oxalate)3]- salts2022

    • Author(s)
      R. Huang*,J. Wu,K. Takahashi,T. Nakamura
    • Organizer
      The 14th International Symposium on Crystalline Organic Metals, Superconductors and Magnets (ISCOM2022)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Molecular machine acts as waterwheel in artificial water channel and isotope effect on water adsorption kinetics2022

    • Author(s)
      S. Li*,K. Takahashi,R. Huang,J. Wu,X. Zheng,C. Xue,S. Noro,I. Hisaki,K. Kokado,T. Nakamura
    • Organizer
      The 14th International Symposium on Crystalline Organic Metals, Superconductors and Magnets (ISCOM2022)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Solvent Dependence of Molecular Motion in Ferromagnetic [Mn(II)Cr(III)(oxalate)3]- Salt2022

    • Author(s)
      J. Wu*,R. Huang,K. Takahashi,T. Nakamura
    • Organizer
      The 14th International Symposium on Crystalline Organic Metals, Superconductors and Magnets (ISCOM2022)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Equilateral and symmetry breaking rare-earth triangles in sandwich-type polyoxometalates regulated by simple organic cations2022

    • Author(s)
      D. Wu*,K. Takahashi,R. Huang,C. Xue,T. Nakamura
    • Organizer
      The 14th International Symposium on Crystalline Organic Metals, Superconductors and Magnets (ISCOM2022)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 2,2'-Oxybis(ethylaminium)と[18]crown-6誘導体からなる超分子カチオンを導入した[Ni(dmit)2]塩の結晶構造と負の熱膨張2022

    • Author(s)
      羽田 将人*,高橋 仁徳,蓮尾 直洋,黄 瑞康,薛 晨,中村 貴義
    • Organizer
      第16回分子科学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 分岐鎖アルキルアンモニウム/[18]crown-6誘導体からなる結晶における協同的分子運動と誘電応答2022

    • Author(s)
      金丸 和矢*,高橋 仁徳,黄 瑞康,薛 晨,中村 貴義
    • Organizer
      第16回分子科学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Enhancement of Negative Thermal Expansion and Perturbation of Magnetic Exchange Interaction in [Ni(dmit)2] Salts by Solid-State Molecular Motion2022

    • Author(s)
      K. Takahashi*,C. Xue,R. Huang,T. Nakamura
    • Organizer
      the 44th International Conference on Coordination Chemistry
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Peculiar Magnetic Response and Negative Thermal Expansion of a Nickel Dithiolate Crystal2022

    • Author(s)
      K. Takahashi*,R. Huang,C. Xue,T. Nakamura
    • Organizer
      8th Asian Conference on Coordination Chemistry (ACCC)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Cooperative motion of supramolecular cation composed of branched-chain alkylammonium and dibenzo[18]crown-6 in [Ni(dmit)2] salts induced by removal of crystallized solvent2022

    • Author(s)
      K. Kanamaru*,K. Takahashi,R. Huang,C. Xue,T. Nakamura
    • Organizer
      8th Asian Conference on Coordination Chemistry (ACCC)
    • Related Report
      2022 Annual Research Report
  • [Presentation] Crystal Structure and Thermal Expansion of Monovalent [Ni(dmit)2] Salts with Supramolecular Cation structure Composed of 2,2'-oxybis(ethylaminium+) and [18]crown-62022

    • Author(s)
      M. Haneda*,K. Takahashi,N. Hasuo,R. Huang,C. Xue,T. Nakamura
    • Organizer
      8th Asian Conference on Coordination Chemistry (ACCC)
    • Related Report
      2022 Annual Research Report
  • [Presentation] 2,2’-Oxybis(ethylaminium)([18]crown-6)2[Ni(dmit)2]2の結晶構造と負の熱膨張2022

    • Author(s)
      羽田 将人*,高橋 仁徳,蓮尾 直洋,黄 瑞康,薛 晨,中村 貴義
    • Organizer
      日本化学会北海道支部2022年夏季研究発表会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 2-methylpropylammonium / dibenzo[18]crown-6超分子カチオンを導入した[Ni(dmit)2]塩の結晶溶媒脱離に伴う構造変化と誘電応答2022

    • Author(s)
      金丸 和矢*,高橋 仁徳,黄 瑞康,薛 晨,中村 貴義
    • Organizer
      日本化学会北海道支部2022年夏季研究発表会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Negative Thermal Expansion and Magnetic Properties of [Ni(dmit)2] Crystals with One-Dimensional Column of Supramolecular Cation2022

    • Author(s)
      K. Takahashi,R. Huang,C. Xue,T. Nakamura*
    • Organizer
      International Conference on Science & Technology of Synthetic Metals 2022
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Oxalate-Bridged Bimetallic Ferromagnetic Hybrid Complexes: Crystal Structures2022

    • Author(s)
      J. Wu*,K. Takahashi,Y. Suzuki,S. Nishihara,R. Tsunashima,J. Kawamata,T. Akutagawa,T. Nakamura
    • Organizer
      International Conference on Science & Technology of Synthetic Metals 2022
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Cooperative molecular motion and dielectric response in crystals composed of branched-chain alkylammonium/Dibenzo [18] crown-62022

    • Author(s)
      K. Kanamaru*,K. Takahashi,R. Huang,C. Xue,T. Nakamura
    • Organizer
      23rd RIES-HOKUDAI International Symposium
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Crystal Structure and Negative thermal expansion of [Ni(dmit)2] Salts with 2,2’-Oxybis(ethylaminium)- [18] crown-6 Supramolecular cation2022

    • Author(s)
      M. Haneda*,K. Takahashi,N. Hasuo,R. Huang,C. Xue,T. Nakamura
    • Organizer
      23rd RIES-HOKUDAI International Symposium
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 4-aminopyridinium 分子水車に基づく結晶内水分子輸送2022

    • Author(s)
      高橋 仁徳*,李 思敏,黄 瑞康,薛 晨,野呂 真一郎,中村 貴義
    • Organizer
      第30回有機結晶シンポジウム
    • Related Report
      2022 Annual Research Report
  • [Presentation] Towards molecular multiferroelectrics by supramolecular rotor and ferromagnetic [MnCr(oxalate)3]- salts2022

    • Author(s)
      R. Huang*,W. Jiabing,K. Takahashi,T. Nakamura
    • Organizer
      第30回有機結晶シンポジウム
    • Related Report
      2022 Annual Research Report
  • [Presentation] 結晶内で回転するカチオンのアルキル鎖修飾による熱膨張制御と磁性2022

    • Author(s)
      高橋 仁徳、小門 憲太、黄 瑞康、薛 晨、中村 貴義
    • Organizer
      日本化学会 第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] 分岐鎖アルキルアンモニウム/dibenzo[18]crown-6超分子カチオンを導入した[Ni(dmit)2]塩の構造と物性2022

    • Author(s)
      金丸和矢、高橋 仁徳、小門 憲太、黄 瑞康、薛 晨、中村 貴義
    • Organizer
      日本化学会 第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] Deformation of Supramolecular Cation and Physical Properties of Nickel Dithiolate Magnetic Crystals2021

    • Author(s)
      Kiyonori Takahashi, Takayoshi Nakamura
    • Organizer
      International Symposium on Thermal and Entropic Science for young Thermodynamicists
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] 擬ロタキサン型超分子カチオンの結晶内分子運動と誘電応答2021

    • Author(s)
      広瀬 昂生、高橋 仁徳、小門 憲太、黄 瑞康、薛 晨、中村 貴義
    • Organizer
      第15回分子科学討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] [Ni(dmit)2]塩の特異な磁気挙動と超分子カチオンの固相運動によって促進される負の熱膨張2021

    • Author(s)
      高橋 仁徳、白川 祐基、小門 憲太、黄 瑞康、薛 晨、中村 貴義
    • Organizer
      第15回分子科学討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] [Ni(dmit)2]塩の2つの多形における超分子カチオンの分子運動からの大きなリラクサー型誘電応答2021

    • Author(s)
      Simin Li, Kiyonori Takahashi, Rui-Kang Huang, Chen Xue, Takayoshi Nakamura
    • Organizer
      第15回分子科学討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] 分鎖アルキルアンモニウム/ dibenzo[18]crown-6超分子カチオンの結晶内分子回転2021

    • Author(s)
      金丸 和矢、高橋 仁徳、小門 憲太、黄 瑞康、薛 晨、中村 貴義
    • Organizer
      第15回分子科学討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] Dibenzo[24]crown-8が形成するチャンネル構造内におけるヘテロ5員環カチオンの運動と誘電性2021

    • Author(s)
      堺 博紀、高橋 仁徳、小門 憲太、黄 瑞康、薛 晨、中村 貴義
    • Organizer
      第15回分子科学討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] Solid-state molecular rotation and magnetic properties of nickel dithiolate salts with one-dimensional columnar arrangement of supramolecular cation2021

    • Author(s)
      Kiyonori Takahashi, Ichiro Hisaki, Takayoshi Nakamura
    • Organizer
      The International Chemical Congress of Pacific Basin Societies 2021
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research

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Published: 2021-04-28   Modified: 2024-01-30  

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