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Investigation of physical properties in dimensional crossover complexes with asymmetric components

Publicly Offered Research

Project AreaCoordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
Project/Area Number 17H05366
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionKyoto University

Principal Investigator

大坪 主弥  京都大学, 理学研究科, 助教 (90601005)

Project Period (FY) 2017-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000)
Fiscal Year 2018: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Fiscal Year 2017: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Keywords金属-有機構造体 / ナノチューブ / らせん錯体 / 混合原子価錯体 / プロトン伝導 / 多孔性物質 / 混合原子価 / らせん構造 / キラリティー
Outline of Annual Research Achievements

本研究課題では、近年合成に成功した金属錯体ナノチューブ、人工3重らせん錯体、そして結晶配向性MOFナノ薄膜等の次元クロスオーバー錯体を基盤材料として選択し、キラリティーを導入した非対称内空間を有する金属錯体ナノチューブや、自然分晶する人工らせん錯体を用いた機能性材料の開発を行うことを目的としている。特に、(1)ボトムアップ合成に基づいた金属錯体ナノチューブへの非対称内空間の導入と疎水性/親水性の精密制御、非対称内空間に基づいた新規のプロトン(水分子)ダイナミクス、クラスター形成の解明、(2)らせん性(ヘリシティー)を制御した人工3重らせん錯体の薄膜材料を使用した円偏光発光特性・電子物性を有するキラル液晶相の構築を目指す。
これまでに我々は、およそ 0.2~1.5 nmの開口径を有する種々の金属錯体ナノチューブの合成と構造解析に成功しているが、今年度はこれまでの結果をさらに拡張し、より多彩な疎水性空間の設計を行うことを目的として、新規の三角形型環状錯体の合成と、デバイス作成への足掛かりとするために有機溶媒に可溶な金属錯体ナノチューブと3重らせん錯体の合成に取り組んだ。
その結果、パラジウム(II)イオンと4,7-フェナントロリンからなる新規の三角形型環状錯体を合成し、単結晶X線結晶構造解析に成功した。また、長鎖アルキル基を持つ種々の対アニオンを用いた金属錯体ナノチューブや人工3重らせん錯体を合成し、有機溶媒中でも構造を保持していることを確認し、さらには透過型電子顕微鏡によりその一次元構造を直接観測することにも成功した。今後はこれらの材料を薄膜化することで機能性材料の開発に繋げたいと考えている。

Research Progress Status

平成30年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

平成30年度が最終年度であるため、記入しない。

Report

(2 results)
  • 2018 Annual Research Report
  • 2017 Annual Research Report
  • Research Products

    (13 results)

All 2018 2017

All Journal Article (7 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 7 results,  Open Access: 1 results,  Acknowledgement Compliant: 1 results) Presentation (6 results) (of which Int'l Joint Research: 2 results,  Invited: 3 results)

  • [Journal Article] Modular Cavities: Induced Fit of Polar and Apolar Guests into Halogen-Based Receptors2018

    • Author(s)
      Aoki Kentaro、Otsubo Kazuya、Hanan Garry S.、Sugimoto Kunihisa、Kitagawa Hiroshi
    • Journal Title

      Inorganic Chemistry

      Volume: 57 Issue: 11 Pages: 6222-6225

    • DOI

      10.1021/acs.inorgchem.8b01069

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] “Compression of a Flapping Mechanophore Accompanied by Thermal Void Collapse in a Crystalline Phase”2018

    • Author(s)
      T. Yamakado, K. Otsubo, A. Osuka, and S. Saito
    • Journal Title

      Chem. Sci.

      Volume: 140 Issue: 20 Pages: 6245-6248

    • DOI

      10.1021/jacs.8b03833

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Emergence of Surface- and Interface-Induced Novel Structures and Properties in Metal-Organic Framework Thin Films2018

    • Author(s)
      Tomoyuki Haraguchi, Kazuya Otsubo, Hiroshi Kitagawa
    • Journal Title

      Eur. J. Inorg. Chem.

      Volume: 2018 Issue: 16 Pages: 1697-1706

    • DOI

      10.1002/ejic.201701234

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Superprotonic Phase Change to a Robust Phosphonate Metal-Organic Framework2018

    • Author(s)
      Zohreh Hassanzadeh Fard, Norman E. Wong, Christos D. Malliakas, Padmini Ramaswamy, Jared M. Taylor, Kazuya Otsubo, George K. H. Shimizu
    • Journal Title

      Chem. Mater.

      Volume: 30 Issue: 2 Pages: 314-318

    • DOI

      10.1021/acs.chemmater.7b04467

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A highly crystalline oriented metal-organic framework thin film with an inorganic pillar2017

    • Author(s)
      Yuki Watanabe, Tomoyuki Haraguchi, Kazuya Otsubo, Osami Sakata, Akihiko Fujiwara, Hiroshi Kitagawa
    • Journal Title

      Chem. Commun.

      Volume: 53 Issue: 73 Pages: 10112-10115

    • DOI

      10.1039/c7cc03828c

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Fabrication and Structural Characterization of an Ultrathin Film of Two-Dimensional Layered Metal-Organic Framework, {Fe(py)2[Ni(CN)4]} (py: pyridine)2017

    • Author(s)
      Shun Sakaida, Tomoyuki Haraguchi, Kazuya Otsubo, Osami Sakata, Akihiko Fujiwara, Hiroshi Kitagawa
    • Journal Title

      Inorg. Chem.

      Volume: 56 Issue: 14 Pages: 7606-7609

    • DOI

      10.1021/acs.inorgchem.7b01113

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Nanoscale crystalline architectures of Hofmann-type metal-organic frameworks2017

    • Author(s)
      Kazuya Otsubo, Tomoyuki Haraguchi, Hiroshi Kitagawa
    • Journal Title

      Coord. Chem. Rev.

      Volume: in press Pages: 123-138

    • DOI

      10.1016/j.ccr.2017.03.022

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] 次元交差領域における配位性ナノ材料の開発2018

    • Author(s)
      大坪 主弥
    • Organizer
      錯体化学会第68回討論会
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Synthesis and electronic properties of a novel two-legged MX-tube complex with a flexible ligand2018

    • Author(s)
      Kazuya Otsubo, Kunihisa Sugimoto, Shogo Kawaguchi, Hiroshi Kitagawa
    • Organizer
      43rd International Conference on Coordination Chemistry (ICCC2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Ice-tube Formation and High Proton Conduction Realized in Metal-Organic Nanotubes2018

    • Author(s)
      Kazuya Otsubo, Ken-ichi Otake, Kunihisa Sugimoto, Hiroshi Kitagawa
    • Organizer
      The 6th International Conference on Metal-Organic Frameworks & Open Framework Compounds (MOF 2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Creation of Novel Materials Situated in Dimensional Crossover Region and Investigation of Their Physical Properties2018

    • Author(s)
      Kazuya Otsubo
    • Organizer
      日本化学会第98春季年会2018
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] SPring-8の高輝度放射光を利用した 多孔性金属錯体の研究例2018

    • Author(s)
      大坪主弥
    • Organizer
      新学術領域研究「配位アシンメトリ」融合基礎・実習コースセミナー「配位アシンメトリにおける放射光先端計測の利活用法」
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Synthesis and electronic properties of a novel two-legged MX-tube complex with flexible ligand2017

    • Author(s)
      Kazuya Otsubo, Kunihisa Sugimoto, Akihiko Fujiwara, Hiroshi Kitagawa
    • Organizer
      錯体化学会第67回討論会2017
    • Related Report
      2017 Annual Research Report

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Published: 2017-04-28   Modified: 2019-12-27  

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