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CONSTRUCTION OF A SPIN-STATE-SWITCHING MOLECULAR SYSTEM BY USING STRUCTURAL CHANGE OF ELECTROCHROMIC MOLECULES

Research Project

Project/Area Number 13640577
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 機能・物性・材料
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

ITO Akihiro  KYOTO UNIVERSITY, GRADUATE SCHOOL OF ENGINEERING, INSTRUCTOR, 工学研究科, 助手 (90293901)

Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥4,200,000 (Direct Cost: ¥4,200,000)
Fiscal Year 2002: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2001: ¥3,000,000 (Direct Cost: ¥3,000,000)
KeywordsSPIN-STATE-SWITCHING / TETRAPHENYLETHYLENE / NITROXIDE / QUANTUM CHEMICAL CALCULATIONS / ARYLAMINES / ニトロシド / 芳香族アミン多価カチオン / マクマリーカップリング / トリフェニルアミン
Research Abstract

In order to realize a spin-state-switching molecular system, we have designed suitable molecular systems on the basis of quantum chemical calculations. Moreover, we have prepared the precursors of model molecules, and then have examined the magnetic properties of the cation radicals which are generated after oxidation the precursors.
In addition, we have synthesized several arylamines and have examined the spin electronic states of their cation radicals by using the electron spin resonance (ESR) method. These cation radicals were found to be useful for spin-bearing units of spin-state-switching molecular systems. Considering the results obtained, we have prepared the tetraarylethylene carrying two nitroxide radicals. The resulting compound is a mixture of cis- and traps- isomers, and therefore the ESR spectrum of this molecule can be explained to be a mixture of two kinds of spin-triplet species. As a result of the magnetic susceptibility measurements, a strong intramolecular magnetic interaction exists between the two nitroxide radicals. The electrochemical studies revealed that the dication of this molecule takes a distorted conformation originating from lengthening of the olefinic bond after two-electron oxidation. Actually, the ESR spectrum of the dication showed a hyperfine-structured spectrum consisting of independent mononitroxide radicals. This result indicates that no intramolecular magnetic interaction exists between the two nitroxide radicals.
Furthermore, it was confirmed that the neutral state of this molecule can be retrieved from the dication state by treating with a suitable reducing agent. Hence we could show a typical example of the spin-state-switching molecular systems.

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report

Research Products

(13 results)

All 2003 2002 Other

All Journal Article Publications

  • [Journal Article] Design of High-Spin Organic Molecules : toward Magnrtic Parts in Molecular Electronics2003

    • Author(s)
      A.Ito 他2名
    • Journal Title

      Curr.Appl.Phys. 3巻・2-3号

      Pages: 149-153

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] A Spiro-Fused Triarylaminium Radical Cation with a Triplet Ground State2003

    • Author(s)
      A.Ito 他2名
    • Journal Title

      Angew.Chem.Int.Ed. 42巻・8号

      Pages: 921-924

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] Molecular Desigh toward Spin-Polarized Nano-Wire : Oligomer Model Study2003

    • Author(s)
      A.Ito 他2名
    • Journal Title

      Polyhedron 22巻・14-17号

      Pages: 1829-1836

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] Design of High-Spin Organic Molecules : toward Magnrtic Par is in Molecular Electronics2003

    • Author(s)
      A.Ito, M.Urabe, K.Tanaka
    • Journal Title

      Curr.Appl.Phys. 3-(2-3)

      Pages: 149-153

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] A Spiro-Fused Triarylaminium Radical Cation with a Triplet Ground State2003

    • Author(s)
      A.Ito, M.Urabe, K.Tanaka
    • Journal Title

      Angew.Chem.Int.Ed. 42-(8)

      Pages: 921-924

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] Molecular Design toward Spin-Polarized Nano-Wire : Oligomer Model Study2003

    • Author(s)
      A.Ito, M.Urabe, K.Tanaka
    • Journal Title

      Polyhedron 22-(14-17)

      Pages: 1829-1836

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] Facile Synthesis, Crystal Structures, and High-Spin Cationic States of All-para-Brominated Oligo(N-phynyl-m-aniline)s2002

    • Author(s)
      A.Ito 他4名
    • Journal Title

      J.Org.Chem. 67巻・2号

      Pages: 491-498

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] Tuning Spin-State Preference by Substituents : A Case Study of Thianthrene Dication2002

    • Author(s)
      A.Ito 他3名
    • Journal Title

      J.Phys.Chem.A 106巻・37号

      Pages: 8716-8720

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] Facile Synthesis, Crystal Structures,-and. High-Spin Cationic States of All-para-Brominated Oligo(N-phenyl-m-aniline) s2002

    • Author(s)
      A.Ito, H.Ino, K.Tanaka, K.Kanemoto, T.Kato
    • Journal Title

      J.Org.Chem. 67-(2)

      Pages: 491-498

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] Tuning Spin-State Preference by Substituents : A Case Study of Thianthrene Dication2002

    • Author(s)
      A.Ito, H.Ino, H.Ichiki, K.Tanaka
    • Journal Title

      J.Phys.Chem.A 106-(37)

      Pages: 8716-8720

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Akihiro Ito et al.: "Design of High-Spin Organic Molecules : Toward Magnetic Parts in Molecular Electronics"Current Applied Physics. 3巻・2-3号. 149-153 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Akihiro Ito et al.: "A Spiro-Fused Triarylaminium Radical Cation with a Triplet Ground State"Angewandte Chemie International Edition. 42巻・8号. 921-924 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Akihiro Ito et al.: "Facile Synthesis, Crystal Structures, and High-Spin Cationic States of All-para-Brominated Oligo(N-phenyl-m-aniline)s"The Journal of Organic Chemistry. 67. 491-498 (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-03-31   Modified: 2016-04-21  

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