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Design and Preparation of an Organic Magnetic Metal using Novel pi-Electron System

Research Project

Project/Area Number 07640711
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

IZUOKA Akira  The University of Tokyo, Graduate School of Arts and Sciences, Reserch Associate, 大学院・総合文化研究科, 助手 (90193367)

Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1996: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1995: ¥1,300,000 (Direct Cost: ¥1,300,000)
KeywordsOrganic Magnetic Metal / High Spin Molecule / Ferromagnetic Exchange Interaction / Donor / Radical / Electron Transfer / Electron Spin Resonance (ESR) / 磁性金属 / 基底三重項 / ノトロニルニトロキシド / 電子スピン共鳴 / カチオンラジカル
Research Abstract

Development of organic magnetic metals is one of the most interest investigation for molecular magnetism. In such spin system, it is required a spin correlation between conduction electrons and local spins. We designed a series of open shell donors which are candidate molecules as components of such spin system. The open shell donors are constructed with a donor and a radical unit and they are connected so as to become a cross-conjugate pi-system when one-electron oxidation takes place. Cationdiradicals of the open-shell donors were generated in THF solution by treating with iodine. ESR spectra measurement of them indicated the cationdiradicals are all ground state triplet species. Molecular orbital calculation appeared an unique electronic structure of them to us as follows : They have two orthogonal singly occupied molecular orbitals (SOMOs) with different orbital energies. While coefficients of one SOMO of them distribute over the whole molecule, that of the other one localize only on the radical unit. It is considered that large positive exchange interaction arises at the site hold the coefficients of two SOMOs. We prepared also an open-shell donor composed of two nitronyl nitroxides as the radical unit and tetraphenylphenylenediamine as the donor unit. The ESR study showed that they changed the ground state multiplicity from singlet to quartet through one-electron oxidation. These results indicate that these open-shell donors satisfy one of the required conditions for the components of organic magnetic metals.

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (32 results)

All Other

All Publications (32 results)

  • [Publications] H.Sakurai: "Ground State Triplet Cation Diradicals Generated from N,N-Dimethylamino Nitronyl Nitroxide and Its Homologues through One-Electron Oxidation." Chem.Lett.1996. 879-880 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] D.Shiomi: "One-Dimensional Ferrimagnetic Behavior of a Hetero-Spin Chain in an Organic Crystal as Probed by Susceptibility and Relaxation Time Measurements." Mol.Cryst.Liq.Cryst.278. 279-294 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] R.Kumai: "Ground State Triplet Cation Diradicals Having Non-Degenerated Singly Occupied Molecular Orbitals." Mol.Cryst.Liq.Cryst.279. 133-138 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.M.Matsushita: "Ferromagnetic Spin Ordering along Intermolecular Hydrogen Bonds of a Hydroquinone Derivative Carrying a Nitronyl Nitroxide." Mol.Cryst.Liq.Cryst.279. 139-144 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Nakamura: "Novel Organic Ions of High-Spin States.5.Generation of a Hith-Spin Ground State Anion from an Intramolecularly Spin-Frustrated System" J.Am.Chem.Soc.118. 8684-8687 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Sugawara: "Molecular Magnetism:Present and Future." Mol.Cryst.Liq.Cryst.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J.Nakazaki: "Ground State Spin Multiplicity of Cation Diradicals Derived from Pyrroles Carrying Nitronyl Nitroxide." Mol.Cryst.Liq.Cryst.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Sakurai: "Preparation and Property of Ionic CT Complex of Dimethylamino Nitronyl Nitroxide with DDQ." Mol.Cryst.Liq.Cryst.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Izuoka: "Coexistence of Electric Conductivity and Magnetism in the Ion-Radical Salts of a Cross-Cyclophane Twin Donor." Mol.Cryst.Liq.Cryst.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.M.Matsushita: "Hydrgen-Bonded Organic Ferromagnet." J.Am.Chem.Soc.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Oda: "Theoretical Studies of Magnetic Interactions in 2',5'-Dihydroxyphenyl Nitronyl Nitroxide Crystal." Mol.Cryst.Liq.Cryst.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Sakurai: "Ground State Triplet Cation Diradicals Generated from N,N-Dimethylamino Nitronyl Nitroxide and Its Homologues through One-Electron Oxidation" Chem. Lett.1996. 879-880 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] D.Shiomi: "One-Dimensional Ferrimagnetic Behavior of a Hetero-Spin Chain in an Organic Crystal as Probed by Susceptibility and Relaxation Time Measurements" Mol. Cryst. Liq. Cryst.278. 279-294 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] R.Kumai: "Ground State Triplet Cation Diradicals Having Non-Degenerated Singly Occupied Molecular Orbitals." Mol. Cryst. Liq. Cryst.279. 133-138 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.M.Matsushita: "Ferromagnetic Spin Ordering along Intermolecular Hydrogen Bonds of a Hydroquinone Derivative Carrying a Nitronyl Nitroxide" Mol. Cryst. Liq. Cryst.279. 139-144 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Nakamura: "Novel Organic Ions of High-Spin States. 5. Generation of a High-Spin Ground State Anion from an Intramolecularly Spin-Frustrated System" J.Am. Chem. Soc.118. 8684-8687 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Sugawara: "Molecular Magnetism : Present and Future" Mol. Cryst. Liq. Cryst.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J.Nakazaki: "Ground State Spin Multiplicity of Cation Diradicals Derived from Pyrroles Carrying Nitronyl Nitroxide" Mol. Cryst. Liq. Cryst.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Sakurai: "Preparation and Property of Ionic CT Complex of Dimethylamino Nitronyl Nitroxide with DDQ" Mol. Cryst. Liq. Cryst.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Izuoka: "Coexistence of Electric Conductivity and Magnetism in the Ion-Radical Salts of a Cross-Cyclophane Twin Donor." Mol. Cryst. Liq. Cryst.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.M.Matsushita: "Hydrgen-Bonded Organic Ferromagnet" J.Am. Chem. Soc.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Oda: "Theoretical Studies of Magnetic Interactions in 2', 5'-Dihydroxyphenyl Nitronyl Nitroxide Crystal" Mol. Cryst. Liq. Cryst.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Sakurai: "Ground State Triplet Cation Diradicals Generated from N,N-Dimethylamino Nitronyl Nitroxide and Its Homologues through One-Electron Oxidation." Chem.Lett.1996. 879-880 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] D.Shiomi: "One-Dimensional Ferrimagnetic Behavior of a Hetero-Spin Chain in an Organic Crystal as Probed by Susceptibility and Relaxation Time Measurements." Mol.Cryst.Liq.Cryst.278. 279-294 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] R.Kumai: "Ground State Triplet Cation Diradicals Having Non-Degenerated Singly Occupied Molecular Orbitals." Mol.Cryst.Liq.Cryst.279. 133-138 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.M.Matsushita: "Ferromagnetic Spin Ordering along Intermolecular Hydrogen Bonds of a Hydroquinone Derivative Carrying a Nitronyl Nitroxide." Mol.Cryst.Liq.Cryst.279. 139-144 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Nakamura: "Novel Organic Ions of High-Spin States.5.Generation of a High-Spin Ground State Anion from an Intramolecularly Spin-Frustrated System" J.Am.Chem.Soc.118. 8684-8687 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Sugawara: "Molecular Magnetism:Present and Future." Mol.Cryst.Liq.Cryst.(in press).

    • Related Report
      1996 Annual Research Report
  • [Publications] J.Nakazaki: "Ground State Spin Multiplicity of Cation Diradicals Derived from Pyrroles Carrying Nitronyl Nitroxide." Mol.Cryst.Liq.Cryst.(in press).

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Sakurai: "Preparation and Property of Ionic CT Complex of Dimethylamino Nitronyl Nitroxide with DDQ." Mol.Cryst.Liq.Cryst.(in press).

    • Related Report
      1996 Annual Research Report
  • [Publications] Jun Tanaka: "Three-Dimensional Sulfur-Based π-Donor:A Novel Dimeric TTF Derivative of Cross-Cyclophane Thpe" Chemistry Letters. 1995. 579-580 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Akira Izuoka: "Crystal Designing Organic Ferrimagnets" Adv.Mater.7. 672-674 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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