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Research on Combinatorial Functions of Integrated Organic Redox Systems and their Applications for Unimolecular Memory

Research Project

Project/Area Number 15350019
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionHokkaido University

Principal Investigator

SUZUKI Takanori  Hokkaido University, Graduate School of Science, Professor, 大学院・理学研究科, 教授 (70202132)

Co-Investigator(Kenkyū-buntansha) FUJIWARA Kenshu  Hokkaido University, Graduate School of Science, Associate Professor, 大学院・理学研究科, 助教授 (20222268)
Project Period (FY) 2003 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥13,400,000 (Direct Cost: ¥13,400,000)
Fiscal Year 2005: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2004: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 2003: ¥7,500,000 (Direct Cost: ¥7,500,000)
KeywordsMolecular Device / Redox System / Unimolecular Memory / Dynamic Redox System / Dynamic Mesophase / Organogel / Polycation / Polyether / 電子供与体 / 応答性分子 / 記録材料 / 分子エレクトロニクス / 色素 / C-H--O水素結合 / C-H・・・O水素結合
Research Abstract

This project has been planned to develop new design concepts on the novel organic responding molecules based on the integration of redox active molecules. The major themes to be tackled with are as follows : (1) Redox response systems with electrochemical bistability and surface modifying properties ; (2) New synthetic strategy for the fused- polyether structures ; (3) Redox active molecules with phase transition properties triggered by external stimuli.
We have succeeded in preparing redox systems to meet the requirement in the first theme, and some of them are further endowed with multi-input and multi-output fuctionalities. The disuflide unit or ethynyl groups were selected that act as surface-binding linkers for Au an Si, respectively. Preparation of SAM and examination toward the realization of unimolecular memory are now under way.
The fused-polyether skeleton found in some marine natural products should be a suitable motif for studying the aggregation by weak C-H--O hydrogen bonds … More . In the second theme, facile and general convergent strategy was developed for a variety of polyether skeleton. Based on the newly developed protocol based on the reaction between an aldehyde and an acylanion equivalent, we could synthesize polyetheral natural product (hemibrevetoxin B) and the large segments of ciguatoxins with 4-5 ether units. X-ray analyses on some of them have revealed that several short C-H--O contacts were observed that connect tape-shaped polyethers tol the stacked or dimeric strucures. Not only natural but also non-natural polyethers are shown worth investigated.
Reversible oligomerization of bis(diarylethenyl)arenes-type electron donors upon oxidation is the outstanding achievement in terms of the third theme. Deeply-colored polycation oligomers could be isolated as stable salts that regenerated the starting monomeric donors upon reduction. By attaching long alkyl chains on the aryl groups, some of these materials act as organic gelators, thus giving a new desing concept for the dynamic mesophase, whose properties can be modulated by electrochemical input. Less

Report

(4 results)
  • 2005 Annual Research Report   Final Research Report Summary
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (27 results)

All 2006 2005 2004 Other

All Journal Article (20 results) Publications (7 results)

  • [Journal Article] Changes in Conformation upon Complexation of Double-armed Terephthalamide Hosts : Dynamic Molecular Recognition of Ditopic Guests with Strong CD Signaling2006

    • Author(s)
      R.Katoono
    • Journal Title

      Tetrahedron Lett. 47(10)

      Pages: 1513-1518

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Changes in Conformation upon Complexation of Double-armed Terephthalamide Hosts : Dynamic Molecular Recognition of Ditopic Guest with Strong CD Signaling2006

    • Author(s)
      R.Katoono
    • Journal Title

      Tetrahedron Lett. 47(10)

      Pages: 1513-1518

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Isolation and Low-temperature X-ray Analysis of Intramolecular Triarylmethane-Triarylmethylium Complex : Preference of C-H Bridged Unsymmetric Structure Exhibiting Facile 1,5-Hydride Shift and Charge-Transfer Interaction2005

    • Author(s)
      H.Kawai
    • Journal Title

      J. Am. Chem. Soc. 127(35),

      Pages: 12172-12173

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Exceptionally Large Difference in Bond Length among Conformational Isomorphs of a Hexaphenylethane Derivative with a Dispiropyracene Skeleton2005

    • Author(s)
      H.Kawai
    • Journal Title

      Cryst. Growth Des. 5(6)

      Pages: 2256-2260

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Multipoint Recognition of Catecholamines by Hydrindacene-Based Receptors Accompanied by the Complexation-Induced Conformational Switching2005

    • Author(s)
      H.Kawai
    • Journal Title

      Chem. Eur. J. 11(3)

      Pages: 815-824

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Tetracyanoanthraquinodimethanes with a Chiral Amide Group : Preparation, Properties, and Charge-Transfer Photochirogenetic Reaction with 1,2-Dianisylacenaphthene-1,2-diol2005

    • Author(s)
      T.Suzuki
    • Journal Title

      J. Org. Chem. 70(14)

      Pages: 5592-5598

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Stereospecific Change in Conformation upon Complexation of an Exoditopic Tetraamide Host with a Bis(ammonium) Guest : Chiral Recognition and Strong CD Signaling2005

    • Author(s)
      R.Katoono
    • Journal Title

      Chem. Commun. (41)

      Pages: 5154-5156

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Isolation and Low-temperature X-ray Analysis of Intramolecular Triarylmethane-Triarylmethylium Complex : Preference of C-H Bridged Unsymmetric Structure Exhibiting Facil 1,5-Hydride Shift and Charge-Transfer Interaction2005

    • Author(s)
      H.Kawai
    • Journal Title

      J.Am.Chem.Soc. 127(35)

      Pages: 12172-12173

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Exceptionally Large Difference in Bond Length among Conformational Isomorphs of a Hexaphenylethane Derivative with a Dispiropyracene Skeleton2005

    • Author(s)
      H.Kawai
    • Journal Title

      Cryst.Growth Des. 5(6)

      Pages: 2256-2260

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Multipoint Recognition of Catecholamines by Hydrindacene-Based Receptors Accompanied by the Complexation-Induced Conformational Switching2005

    • Author(s)
      H.Kawai
    • Journal Title

      Chem.Eur.J. 11(3)

      Pages: 815-824

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Tetracyanoanthraquinodimethanes with a Chiral Amide Group : Preparation, Properties, and Charge-Transfer Photochirogenetic Reaction with 1,2-Dianisylacenaphthene-1,2-diol2005

    • Author(s)
      T.Suzuki
    • Journal Title

      J.Org.Chem. 70(14)

      Pages: 5592-5598

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Stereospecific Change in Conformation upon Complexation of an Exoditopic Tetraamide Host with a Bis (ammonium) G Chiral Recognition and Strong CD Signaling2005

    • Author(s)
      R.Katoono
    • Journal Title

      Chem.Commun. (41)

      Pages: 5154-5156

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Isolation and Low-temperature X-ray Analysis of Intramolecular Triarylmethane-Triarylmethylium Complex : Preference of C-H Bridged Unsymmetric Structure Exhibiting Facile 1,5-Hydride Shift and Charge-Transfer Interaction2005

    • Author(s)
      H.Kawai
    • Journal Title

      J.Am.Chem.Soc. 127(35),

      Pages: 12172-12173

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Stereospecific Change in Conformation upon Complexation of an Exoditopic Tetraamide Host with a Bis(ammonium) Guest : Chiral Recognition and Strong CD Signaling2005

    • Author(s)
      R.Katoono
    • Journal Title

      Chem.Commun. (41)

      Pages: 5154-5156

    • Related Report
      2005 Annual Research Report
  • [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 10,1O'-Dimethylbiacridan"Tetrahedron Lett.. 44. 6837-6840 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.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

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Published: 2003-04-01   Modified: 2016-04-21  

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