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2018 Fiscal Year Annual Research Report

単一有機分子nビットメモリ及び抵抗可変型分子ワイヤの提案とそのプロトタイプの創成

Research Project

Project/Area Number 15H03790
Research InstitutionHokkaido University

Principal Investigator

鈴木 孝紀  北海道大学, 理学研究院, 教授 (70202132)

Co-Investigator(Kenkyū-buntansha) 上遠野 亮  北海道大学, 理学研究院, 助教 (60432142)
Project Period (FY) 2015-04-01 – 2020-03-31
Keywords分子メモリ / 動的酸化還元 / 分子ワイヤ
Outline of Annual Research Achievements

本研究提案で申請者は、分子エレクトロニクスに対して構造有機化学的アプローチを行うこととし、新たな作用機序にて動作する「有機π電子系の分子メモリ設計指針の提案」と「プロトタイプ分子の構築とその基本動作達成」を通じて、「単一有機分子nビット」という新概念を確立することを目的とした研究を展開している。その際、高い電気化学的双安定性を持ち、中性状態と荷電状態の電子交換が起こらないdyrex(動的酸化還元)骨格を活用し、またdyrex骨格がn個連結された有機分子とすることで、1分子がnビットを担う分子を提案創生する。dyrex骨格や連結リンカーの最適化を経て、リニア連結型、及び二次元連結型(デンドリマ様及びハニカム様連結型)オリゴマーの構築へと展開する計画である。
抵抗可変型分子ワイヤの提案とそのプロトタイプの創成を目指す検討の中で、フェニレン基およびエチニレン基が直鎖上に連結されたπ型分子ワイヤを設計し、全長が約3nmに至る分子の合成に成功した。そのπ系に対して電気化学的刺激によってビフェニル骨格のねじれ角が大きく変化するスイッチングユニットを組み込み、そのユニットの個数によって分子ワイヤ全体での共役が、酸化還元前後でどのように変化するかを調べた。DFT計算による最適化構造の特定や、紫外可視吸収スペクトルの変化を長さの異なるワイヤ型分子で比較することで、目的とした分子ワイヤのモデルが構築できたことを確認した。

Current Status of Research Progress
Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

おおむね順調に進展している

Strategy for Future Research Activity

最終年度には、これまで開発してきた分子群について、molecular junctionなどのデバイス化とその特性調査について鋭意検討を進める計画である。junctionの形成と測定については、National University of SingaporeのChristian A. Nijhuis教授との共同研究を推進する。

  • Research Products

    (20 results)

All 2019 2018 Other

All Int'l Joint Research (1 results) Journal Article (17 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 17 results) Presentation (2 results) (of which Invited: 2 results)

  • [Int'l Joint Research] Nanjing University(中国)

    • Country Name
      CHINA
    • Counterpart Institution
      Nanjing University
  • [Journal Article] Dual dynamic chirality generated in the assembly of three achiral rods through the three-fold twisting of a macrocycle2019

    • Author(s)
      Katoono Ryo、Sakamoto Kazuki、Suzuki Takanori
    • Journal Title

      Chemical Communications

      Volume: 55 Pages: 5503~5506

    • DOI

      DOI: 10.1039/C9CC02226K

    • Peer Reviewed
  • [Journal Article] Chiral diversification through the assembly of achiral phenylacetylene macrocycles with a two-fold bridge2019

    • Author(s)
      Katoono Ryo、Kusaka Keiichi、Saito Yuki、Sakamoto Kazuki、Suzuki Takanori
    • Journal Title

      Chemical Science

      Volume: 10 Pages: 4782~4791

    • DOI

      10.1039/C9SC00972H

    • Peer Reviewed
  • [Journal Article] Synthesis of the cyclohexene segment of portimine2019

    • Author(s)
      Saito Takafumi、Fujiwara Kenshu、Kondo Yoshihiko、Akiba Uichi、Suzuki Takanori
    • Journal Title

      Tetrahedron Letters

      Volume: 60 Pages: 386~389

    • DOI

      10.1016/j.tetlet.2018.12.063

    • Peer Reviewed
  • [Journal Article] Selective Formation of a Mixed‐valence State from Linearly‐bridged Oligo(aromatic diamines): Drastic Structural Change into a Folded Columnar Stack for Half‐filled Polycations**2019

    • Author(s)
      Nojo Wataru、Ishigaki Yusuke、Takeda Takashi、Akutagawa Tomoyuki、Suzuki Takanori
    • Journal Title

      Chemistry A European Journal

      Volume: - Pages: -

    • DOI

      10.1002/chem.201901272

    • Peer Reviewed
  • [Journal Article] Total synthesis of kehokorins A and B2019

    • Author(s)
      Fujiwara Kenshu、Motousu Ryosuke、Sato Daisuke、Kondo Yoshihiko、Akiba Uichi、Suzuki Takanori、Tokiwano Tetsuo
    • Journal Title

      Tetrahedron Letters

      Volume: 60 Pages: 1299~1301

    • DOI

      10.1016/j.tetlet.2019.04.011

    • Peer Reviewed
  • [Journal Article] Two-way Chromic Systems Based on Tetraarylanthraquinodimethanes: Electrochromism in Solution and Mechanofluorochromism in a Solid State.2019

    • Author(s)
      Y. Ishigaki, K. Sugawara, M. Yoshida, M. Kato, T. Suzuki
    • Journal Title

      Bull. Chem. Soc. Jpn.

      Volume: - Pages: -

    • DOI

      10.1246/bcsj.20190094

    • Peer Reviewed
  • [Journal Article] Engineering of Electrochromic Materials as Activatable Probes for Molecular Imaging and Photodynamic Therapy2018

    • Author(s)
      Wu Luyan、Sun Yidan、Sugimoto Keisuke、Luo Zhiliang、Ishigaki Yusuke、Pu Kanyi、Suzuki Takanori、Chen Hong-Yuan、Ye Deju
    • Journal Title

      Journal of the American Chemical Society

      Volume: 140 Pages: 16340~16352

    • DOI

      10.1021/jacs.8b10176

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Direct synthesis of aryl-annulated [c]carbazoles by gold(i)-catalysed cascade reaction of azide-diynes and arenes2018

    • Author(s)
      Kawada Yuiki、Ohmura Shunsuke、Kobayashi Misaki、Nojo Wataru、Kondo Masaki、Matsuda Yuka、Matsuoka Junpei、Inuki Shinsuke、Oishi Shinya、Wang Chao、Saito Tatsuo、Uchiyama Masanobu、Suzuki Takanori、Ohno Hiroaki
    • Journal Title

      Chemical Science

      Volume: 9 Pages: 8416~8425

    • DOI

      10.1039/C8SC03525C

    • Peer Reviewed
  • [Journal Article] Expandability of a long C-O bond by a scissor effect in acenaphthofuran2018

    • Author(s)
      Uchimura Yasuto、Shimajiri Takuya、Ishigaki Yusuke、Katoono Ryo、Suzuki Takanori
    • Journal Title

      Chemical Communications

      Volume: 54 Pages: 10300~10303

    • DOI

      10.1039/C8CC05998E

    • Peer Reviewed
  • [Journal Article] Molecular Wires with Controllable π-Delocalization Incorporating Redox-Triggered π-Conjugated Switching Units2018

    • Author(s)
      Nojo Wataru、Tamaoki Hitomi、Ishigaki Yusuke、Katoono Ryo、Fujiwara Kenshu、Fukushima Takanori、Suzuki Takanori
    • Journal Title

      ChemPlusChem

      Volume: - Pages: -

    • DOI

      10.1002/cplu.201800341

    • Peer Reviewed
  • [Journal Article] Transmission of Point Chirality to Axial Chirality for Strong Circular Dichroism in Triarylmethylium-o,o-dimers2018

    • Author(s)
      Suzuki Takanori、Ishigaki Yusuke、Iwai Tomohiro、Hayashi Yuki、Nagaki Aiichiro、Katoono Ryo、Fujiwara Kenshu、Yoshida Jun-ichi
    • Journal Title

      Synlett

      Volume: 29 Pages: 2147~2154

    • DOI

      10.1055/s-0037-1610190

    • Peer Reviewed
  • [Journal Article] Double bond formation based on nitroaldol reaction and radical elimination: A prototype segment connection method for the total synthesis of nigricanoside A dimethyl ester2018

    • Author(s)
      Tsunoda Takayuki、Fujiwara Kenshu、Okamoto Satoshi、Kondo Yoshihiko、Akiba Uichi、Ishigaki Yusuke、Katoono Ryo、Suzuki Takanori
    • Journal Title

      Tetrahedron Letters

      Volume: 59 Pages: 1846~1850

    • DOI

      10.1016/j.tetlet.2018.03.091

    • Peer Reviewed
  • [Journal Article] Narrower HOMO-LUMO gap attained by conformational switching through peripheral polyarylation in 1,4,5,8-tetraaza-9,10-anthraquinodimethanes2018

    • Author(s)
      Suzuki Takanori、Ishigaki Yusuke、Sugawara Kazuma、Umezawa Yu、Katoono Ryo、Shimoyama Atsushi、Manabe Yoshiyuki、Fukase Koichi、Fukushima Takanori
    • Journal Title

      Tetrahedron

      Volume: 74 Pages: 2239~2244

    • DOI

      10.1016/j.tet.2018.03.041

    • Peer Reviewed
  • [Journal Article] Enhanced circular dichroism at elevated temperatures through complexation-induced transformation of a three-layer cyclophane with dualistic dynamic helicity2018

    • Author(s)
      Katoono Ryo、Obara Yudai、Fujiwara Kenshu、Suzuki Takanori
    • Journal Title

      Chemical Science

      Volume: 9 Pages: 2222~2229

    • DOI

      10.1039/C7SC05242A

    • Peer Reviewed
  • [Journal Article] Supramolecular chiroptical switching of helical-sense preferences through the two-way intramolecular transmission of a single chiral source2018

    • Author(s)
      Katoono Ryo、Kusaka Keiichi、Tanaka Yuki、Fujiwara Kenshu、Suzuki Takanori
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 16 Pages: 1167~1171

    • DOI

      10.1039/C7OB03057F

    • Peer Reviewed
  • [Journal Article] Longest C-C Single Bond among Neutral Hydrocarbons with a Bond Length beyond 1.80A2018

    • Author(s)
      Ishigaki Yusuke、Shimajiri Takuya、Takeda Takashi、Katoono Ryo、Suzuki Takanori
    • Journal Title

      Chem

      Volume: 4 Pages: 795~806

    • DOI

      10.1016/j.chempr.2018.01.011

    • Peer Reviewed
  • [Journal Article] Dynamic or undynamic chirality generated by helical arrangement of a shape-persistent ring and rod doubly bridged in a molecule2018

    • Author(s)
      Katoono Ryo、Obara Yudai、Kusaka Keiichi、Suzuki Takanori
    • Journal Title

      Chemical Communications

      Volume: 54 Pages: 735~738

    • DOI

      10.1039/C7CC09485J

    • Peer Reviewed
  • [Presentation] Studies on Dynamic Redox Systems: Construction of Record-breaking Strained Compounds and Development of Unimolecular Memory2019

    • Author(s)
      鈴木孝紀
    • Organizer
      第99回日本化学会春季年会(受賞講演)
    • Invited
  • [Presentation] 超結合:共有結合の限界を超えた化学2019

    • Author(s)
      鈴木孝紀
    • Organizer
      第99回日本化学会春季年会(特別企画)
    • Invited

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Published: 2019-12-27  

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