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不斉表面の電気化学的応答とその機能

Research Project

Project/Area Number 14654139
Research Category

Grant-in-Aid for Exploratory Research

Allocation TypeSingle-year Grants
Research Field 物質変換
Research InstitutionHokkaido University

Principal Investigator

鈴木 孝紀  北海道大学, 大学院・理学研究科, 教授 (70202132)

Project Period (FY) 2002 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 2004: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2003: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2002: ¥1,100,000 (Direct Cost: ¥1,100,000)
Keywords酸化還元系 / 応答性分子 / 分子不斉 / 色素 / 円二色性 / 分子素子 / 表面修飾 / 電気化学 / トリチル / ジカチオン
Research Abstract

本研究課題の目的は、1)不斉要素を有する有機酸化還元系の構築とその応答機能を開発し、2)それらを表面へと固定できる方法論を応用して表面物性としての機能を引き出すことにある。本年度はそれぞれ、1)テトラヒドロフェナントラアゼピン骨格を有する系の開発、2)表面修飾に利用できるアンカー置換基を有する酸化還元系の開発について検討を行った。
a)アゼピン骨格を有するキラルな酸化還元系:不斉要素を有する有機酸化還元系は、電気化学的入力に対して電子スペクトル及び円二色性(CD)スペクトルの双方の出力を与える多重出力型分子応答系となる。大きなCD出力を得るためには、エキシトンカップリングの利用できる軸不斉またはらせん状化合物が望ましい。表題骨格のヘリシティは容易に反転するが、N上にキラルなベンジルアミノ基を導入することで一方のジアステレオマーを優先させることに成功した。これにより、煩雑な光学分割を行わずに感度良くエレクトロキロオプティカル出力が得られる系の構築が可能となった。
b)末端アセチレンおよびジスルフィド官能基をする酸化還元系:表面での自己組織化膜の形成を行うためには、表面修飾に利用できるアンカー置換基が導入された機能性酸化還元系を合成する必要がある。これまで動的酸化還元活性が確認されたジスピロジヒドロフェナントレン骨格を有する3種の酸化還元対の、a)ベイ領域へのエチニル基に導入、b)スピロ環上へのプロパルギル基の導入、c)ベイ領域へのジスルフィド官能基の導入された化合物の合成に成功した。前2者は水素終端シリコン表面への固定に、後者は金表面への固定に利用できる官能基を有するものであり、現在膜の調製の検討を行っている。

Report

(3 results)
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (19 results)

All 2005 2004 Other

All Journal Article (6 results) Publications (13 results)

  • [Journal Article] Multipoint Recognition of Catecholamines by Hydrindacene-Based Receptors Accompanied by the Complexation-Induced Conformational Switching2005

    • Author(s)
      H.Kawai, R.Katoono, K.Fujiwara, T.Tsuji, T.Suzuki
    • Journal Title

      Chem.Eur.J. 11

      Pages: 815-824

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Dynamic redox systems based on bis(spiroxanthene)-type donors with a polycyclic aromatic hydrocarbons : Preparation, X-ray structures and electrochromic response with fluorescence2004

    • Author(s)
      T.Suzuki, S.Tanaka, H.Higuchi, H.Kawai, K.Fujiwara
    • Journal Title

      Tetrahedron Lett. 45

      Pages: 8563-8567

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Pyrazino-tetracyanonaphthoquinodimethanes : Sterically Deformed Electron Acceptors Affording Zwitterionic Radicals2004

    • Author(s)
      T.Suzuki, S.Miyanari, H.Kawai, K.Fujiwara T.Fukushima, T.Miyashi, Y.Yamashita
    • Journal Title

      Tetrahedron 60

      Pages: 1997-2003

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Positive Homotropic Allosteric Binding of Benzenediols in a Hydrindacene-Based Exoditopic Receptor : Cooperativity in Amide Hydrogen Bonding2004

    • Author(s)
      H Kawai, R.Katoono, K.Nishimura, S.Matsuda, K.Fujiwara, T.TsuJi, T.Suzuki
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 5034-5035

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Formal Total Synthesis of Hemibrevetoxin B by a Convergent Strategy2004

    • Author(s)
      K.Fujiwara, D.Sato, M.Watanabe, H.Morishita, A.Murai, H.Kawai, T.Suzuki
    • Journal Title

      Tetrahedron Lett. 45

      Pages: 5243-5246

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Convergent Synthesis of the ABCDE-ring Part of Ciguatoxin CTX3C2004

    • Author(s)
      K.Fujiwara, A.Goto, D.Sato, Y.Ohtaniuchi, H.Tanaka, A.Murai, H.Kawai, T.Suzuki
    • Journal Title

      Tetrahedron Lett. 45

      Pages: 7011-7014

    • Related Report
      2004 Annual Research Report
  • [Publications] H.Higuchi, E.Ohta, H.Kawai, K.Fujiwara, T.Tsuji, T.Suzuki: "Electrochiroptical Response of 2,2'-(2,2-Diarylethenyl)binaphthyl-type Electron Donors That Undergo Reversible C-C Bond Formation/Breaking upon Two-electron Transfer"J.Org.Chem.. 68. 6605-6610 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Suzuki, A.Migita, H.Higuchi, H.Kawai, K.Fujiwara, T.Tsuji: "A Novel Redox Switch for Fluorescence : Drastic UV-Vis and Fluorescence Spectral Changes upon Electrolysis of a Hexaphenylethane Ferivative of 10,10'Dimethylbiacridan"Tetrahedron Lett.. 44. 6837-6840 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Suzuki, T.Nagasu, H.Kawai, K.Fujiwara, T.Tsuji: "Formation of Keto-carbeniums from 1,2,2-Triarylacenaphthen-1-ols by Breaking a Long C-C bond : Unusual Alcohol Protonolysis Accompanied by Formal Hydride Abstraction"Tetrahedron Lett.. 44. 6095-6098 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Suzuki, Y.Tsubata, Y.Obana, T.Fukushima, T.Miyashi, M.Saito, H.Kawai, K.Fujiwara, K.Akiyama: "4,7-Bis(dimethylamino)benzimidazoles and Twin-type Derivatives : Reversible Two-stage Redox System Modulated by Proton-transfer"Tetrahedron Lett.. 44. 7881-7844 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Suzuki, M.Saito, H.Kawai, K.Fujiwara, T.Tsuji: "Preparation, Properties and X-ray Structures of 5,5'-Bi(8-aminoquinoxalyl)s : Novel Wurster-type Electron Donors with a Heterobiaryl skeleton"Tetrahedron Lett.. 45. 329-333 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Tsuji, M.Okuyama, M.Ohkita, H.Kawai, T.Suzuki: "Functionalization and Kinetic Stabilization of the [4]Paracyclophane System and Aromaticity of Its Extremely Bent Benzene Ring"J.Am.Chem.Soc.. 125. 951-961 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Suzuki, H.Higuchi, T.Tsuji, J.Nishida, Y.Yamashita, T.Miyashi: "Chemistry of Nanomolecular System : Toward the Realization of Molecular Device ; Dynamic Redox Systems : Toward the Realization of Unimolecular Memory (T.Nakamura, T.Matsumoto, H.Tada, K.Sugiura)"193 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Suzuki, R.Yamamoto, H.Higuchi, M.Ohkita, T.Tsuji: "Electrochiroptical Response of a Hexaarylethane Derivatives with a Helical π-Skeleton : Drastic UV-Vis and CD Spectral Changes upon Electrolysis of 4',5'-Dibromodispiro[xanthene-9,9'(9'H,10'H)-phenanthrene-10',9"-xanthene]"J. Chem. Soc., Perkin Trans. 2. 1937-1942 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Suzuki, J.Nishida, E.Hirota, M.Ohkita, T.Tsuji: "Chiral Electron Donors and Acceptors : Novel "Electrochiroptical" Response"Synth. Met.. (印刷中). (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 西田純一, 鈴木孝紀, 辻孝: "ヘキサフェニルエタン型化合物を基軸とした酸化還元型応答系の構築"有機合成化学協会誌. Vol.60. 40-51 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Ohkita, M.Kawano, T.Suzuki, T.Tsuji: "Supramolecular Graphyne : a C'(sp)-H・・・N Hydrogen-bonded Unique Network Structure of 2,4,6-Triethynyl-1,3,5-triazine"Chem. Commun.. 3054-3055 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Tsuji, M.Okuyama, M.Ohkita, H.Kawai, T.Suzuki: "Functionalization and Kinetic Stabilization of the [4]Paracyclophane System and Aromaticity of Its Extremely Bent Benzene Ring"J. Am. Chem. Soc.. Vol.125. 951-961 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Suzuki, H.Higuchi, T.Tsuji, J.Nishida, Y.Yamashita, T.Miyashi: "Chemistry of Nanomolecular Systems : Toward the Realization of Molecular Device, Chapter 1 Dynamic Redox Systems : Toward the Realization of Unimolecular Memory"T.Nakamura, T.Matsumoto, H.Tada, K.Sugiura, (Springer). 113 (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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