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Spin Alignment in Model Molecules for Organic Ferrimagnets as Studied by ENDOR/TRIPLE Spectroscopy

Research Project

Project/Area Number 02453014
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 物理化学一般
Research InstitutionOsaka City University

Principal Investigator

ITOH Koichi  Osaka City Univ., Dept. of Chem., Prof., 理学部, 教授 (70029403)

Co-Investigator(Kenkyū-buntansha) TAKUI Takeji  Osaka City Univ., Dept. of Chem, Prof., 理学部, 教授 (10117955)
Project Period (FY) 1990 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥4,700,000 (Direct Cost: ¥4,700,000)
Fiscal Year 1992: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1991: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1990: ¥2,800,000 (Direct Cost: ¥2,800,000)
KeywordsOrganic ferrimagnets / Unusually large negative spin polarization / Organic molecular based magnetism / ENDOR / TRIPLE / pi Topoology / Spin multiplet-multiplet interaction / Hetero-spin systems / Spin chemistry / 有機フェリ磁性 / 複合型高スピン分子 / 電子核ー核三重共鳴 / スピン密度分布 / 次世代テクノロジ- / 有機磁性 / 分子性磁性 / 有機強磁性高分子 / 有機フェリ磁性高分子 / トポロジ-的対称性 / 電子一核二重共鳴 / 負のスピン分極
Research Abstract

Organic molecular based magnetism has been the focus of current topics in many fields of both pure and applied sciences. It is of crucial importance to substantiate the possible occurrence of various types of purely organic magnetism, particularly purely organic ferrimangetism which is defined as antiferromagnetically coupled organic hetero-spin assemblages with coherence length of long range.
This program deals with the topologically spin-controlled molecular design and spin structure of the first organic hetero-spin system, 4-(diphenylmethylene)-4'-(m-phenylenebis (phenylmethylene)-ether 1, in which non-identical spins (S_i=1 and S_j=2) couple antiferromagnetically via an ether bridge in the ground state. The hetero spin system is a model for purely organic ferrimagnets via through-bond approaches, in which the underlining magnetic coupling is superexchange interaction via the bridge. The concept of the molecular design under study is associated with a counterpart of crystalline ferrimagnets via through-space approaches commonly exploited in magnetic materials. The single-crystal ENDOR spectroscopy has been applied to 1, featuring an unusually large negative spin polarization in the spin density distribution for the ground state (S=1). The finding discloses a physical insight into organic ferrimagnetism. The unusual negative spin polarization strictly arises from a salient feature of organic hetero-spin systems in the electronic ground state, directly showing that one molecular spin moiety with S_i (S_j=1) is inverted against the another with an inequivalent spin S_j (S_j=2) in antiferromagnetically coupled hetero-spin systems. The spin-inversion is responsible for such an unusually large negative spin polarization that chemistry so far has never expected. It is referred to a new aspect of negative spin polarization in chemistry.

Report

(4 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • 1990 Annual Research Report
  • Research Products

    (60 results)

All Other

All Publications (60 results)

  • [Publications] Y.Miura: "Molecular Design,Synthesis and Magnetic Characterization of Poly-(phenylacetylene)with-Toporegulated Pendant Nitronyl radicals as Models for Organic Superpara-and Ferro-Magnets" J.Polym.Sci. 30. 956-966 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Matsushita: "Novel Organic Ions of High-Spin States II:Determination of the Spin Multiplicity of the Ground State and ^1H-ENDOR Study of the Monoanion of m-Phenylenebis(phenylmethylene)" J.Am.Chem.Soc.114. 7470-7475 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Teki: "Topology and Spin Alignment in a Novel Organic High-Spin Molecule Bipheny1-3,4'-bis(phenylmethylene),as Studied by ESR and a generalized UHF Hubbard Calculation" J.Am.Chem.Soc.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Teki: "Topology and Spin Alignment in Organic Hihg-Spin Molecules" Bull.Magn.Reson.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] K.Furukawa: "Molecular Design,Synthesis,and Electron Spin Resonance Detection of a Ground-States Tridecet (S=6)Hydrocarbon as a Model for 2D Organic Ferro-and Superpara-Magnets" Bull.Magn.Reson.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Takui: "Organic High-Spin State ENDOR/TRIPLE Spectroscopy:Spin and Molecular Structural Studies of Models for Organic Ferro-and Ferri-Magnets" Bull.Magn.Reson.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Teki: "Role of the Spin Correlation and weakly Interacting Model for the Spin Alignment in Organic High-Spin Molecules" Mol.Cryst.Liq.Cryst.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] K.Sato: "Spin Polarization Effect in Organic High-Spin Molecules,as StuDied by Singli Crystal ESR and ^1H-ENDOR Spectroscopies" Mol.Cryst.Liq.Cryst.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] K.Furukawa: "Molecular Design,Synthesis,and Electron Spin Resonance Detection of a Ground-State Tridecet(S=6)Hydrocarbon as a Model for 2D Organic Ferro-and Superpara-Magnets" Mol.Cryst.Liq.Cryst.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Teki: "Magnetic Behavior of(N-arylthio)-2,4,6-triphenylanilino Radical Crystals" Mol.Cryst.Liq.Cryst.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Miura: "Syntheses of Nitroxide Polyradicals by the Catalytic Polycondensation of 3,5-Diethynylbenzenes Carrying Nitroxide Radicals with Diiodobenzenes and Their Magnetic Characterization" Mol.Cryst.Liq.Cryst.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Teki: "Novel Organic Ions of High-Spin States" Mol.Cryst.liq.Cryst.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Takui: "Unusually Large Negative Spin Polarization of Hetero-Spin Compo-site High-Spin Carbenes as Models for Purely Organic Ferrimag-nets:topological Through-Bond Approaches and ESR/ENDOR Characterization" Mol.Cryst.Liq.Cryst.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Matsushita: "Novel Organic Ions of High-Spin States III.:ESR and ^1H-ENDOR Studies of a Monocation of m-phenylenebis(phenylmethylene)" Bull.Chem.Soc.Jpn.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Miura K. Inui, F. Yamaguchi, M. Inoue, Y. Teki, T. Takui, and K. Itoh: "Molecular Design, synthesis and Magnetic Characterization of Poly(phenylacetylene) with PI-Toporegulated Pendant Nitronyl Radicals as Models for Organic Suerpara- and Ferro-Magnets" J. Polym. Soc.30. 956-966 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M. Matsushita, T. Nakamura, T. Momose, T. Shida, Y. Teki, T. Takui, T. Kinoshita, and K. Itoh: "Novel Organic Ions of High-Spin States II.: Determination of the Spin Multiplicity of the Ground State and ^H-ENDOR Study of the Monoanion of m-Phenylenebis(phenyl-methylene)" J. Am. Chem. Soc.114. 7470-7475 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y. Teki, I. Fujita, T. Kinoshita, T. Takui, and K. Itoh.: "Topology and Spin Alignment in a Novel Organic High-Spin Molecule, Bi-phenyl-3,4'-bis(phenylmenthylene), as Studied by ESR and A generalized UHF Hubbard Calculation" J. Am. Chem. Soc.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y. Teki, K. Sato, M. Okamoto, A. Yamashita, Y. Yamaguchi, T. Takui, T. Kinoshita, and K. Itoh: "Topology and Spin alignment in Organic High-Spin Molecules" Bull. Magn. Reson.14.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] K. Furukawa, T. Matsumura, Y. Teki, T. Kinoshita, T. Takui, and K. Itoh: "Molecular Design,Synthesis and Electron Spin Reson-ance of a Ground-State Tridecet (S=6) HYdrocarbon as a Model for 2D Organic Ferro- and Superpara-Magnets" Bull. Magn. Reson.15.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T. Takui, Y. Teki, M. Endoh, H. Kitai, Y. Okudo, S. Kita, T. Kinoshita, and K. Itoh: "Organic High-Spin State ENDOR/TRIPLE Spectroscopy: Spin and Molecular Structural Studies of Models for Organic Ferro-and Ferri-Magnets" Bull. Magn. Reson.15.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y. Teki, T. Takui, K. Sato, A. Yamashita, M. Okamoto, T. Ki-noshita, and K. Itoh: "Role of the Spin Correlation and Weakly Inter-acting Model for the Spin Alignment in Organic High-Spin Molecules" Mol. Cryst. Liq. Cryst.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] K. Sato, Y. Yamaguchi, Y. Teki, T. Takui, T. Kinoshita, and K. Itoh: "Spin Polarization Effect in Organic High-Spin Molecules, as Studied by Single Crystal ESR and ^1H-ENDOR Spectroscopies" Mol. Cryst. Liq. Cryst.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] K. Furukawa, T. Matsumura, Y. Teki, T. Kinoshita, T. Takui, and K. Itoh: "Molecular Design, Synthesis, and Electron Spin Resonance Detection of a Ground-State Tridecet (S=6) Hydrocarbon as a Model for 2D Organic Ferro-and Superpara-Magnets" Mol. Cryst. Liq. Cryst.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y. Teki, Y. Miura, A. Tanaka, T. Takui, and K. Itoh: "Magnetic Behavior of (N-arylthio)-2,4,6-triphenylanilino Radical Cry-stals" Mol. Cryst. Liq. Cryst.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y. Miura, Y. Ushitani, Y. Ogo, Y.Teki, T. Takui, and K. Itoh: "Syntheses of Nitroxide Polyradicals by the Catalytic Polycondensa-tion of 3,5-Diethynylbenzens Carrying Nitroxide Radicals with Diio-dobenzenes and Their Magnetic Characterization" Mol. Cryst. Liq. Cryst.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y. Teki, T. Takui, T. Kinoshita, K. Itoh, M.Matsushiata, T. Nakmura, T. Momose, and T. Shida: "Novel Organic Ions of High-Spin States" Mol. Cryst. Liq. Cryst.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T. Takui, Y. Teki, M. Endoh, Y. Okudo, T. Kinoshita, and K. Itoh: "Unusually Large Negative Spin Polarization of Hetero-Spin Composite High-Spin Carbenes as Models for Purely Organic Ferrimagnets: Topological Through-Bond Approaches and ESR/ENDOR Characterization" Mol. Cryst. Liq. Cryst.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M. Matsushita, T. Nakamura, T. Momose, T. Shida, Y. Teki, T. Takui, T. Kinoshita, and K. Itoh: "Novel Organic Ions of High-Spin III.: ESR and ^1H-ENDOR Studies of a Monocation of m-phenyl-enebis(phenylmethylene)" Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Miura: "Molecular Design,Synthesis and Magnetic Characterization of poly-(phenylacetylene) with π-Toporegulated Pendant Nitronyl radicals as Models for Organic Superpara-and Ferro-Magnets" J.Polym.Sci. 30. 956-966 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Matsushita: "Novel Organic lons of High-Spin States II:Determination of the Spin Multiplicity of the Ground State and ^1H-ENDOR Study of the Monoanion of m-Phenylenebis(phenylmethylene)" J.Am.Chem.Soc.114. 7470-7475 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Teki: "Topology and Spin Alignment in a Novel Organic High-Spin Molecule Biphenyl-3,4′-bis(phenylmethylene),as Studied by ESR and a generalized UHF Hubbard Calculation" J.Am.Chem.Soc.

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Teki: "Topology and Spin Alignment in Organic High-Spin Molecules" Bull.Magn.Reson.

    • Related Report
      1992 Annual Research Report
  • [Publications] K.Furukawa: "Molecular Design,Synthesis,and Electron Spin Resonance Detection of a Ground-States Tridecet (S=6) Hydrocarbon as a Model for 2D Organic Ferro-and Superpara-Magnets" Bull.Magn.Reson.

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Takui: "Organic High-Spin State ENDOR/TRIPLE Spectroscopy: Spin and Molecular Structural Studies of Models for Organic Ferro-and Ferri-Magnets" Bull.Magn.Reson.

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Teki: "Role of the Spin Correlation and weakly Interacting Model for the Spin Alignment in Organic High-Spin Molecules" Mol.Cryst.Liq.Cryst.

    • Related Report
      1992 Annual Research Report
  • [Publications] K.Sato: "Spin Polarization Effect in Organic High-Spin Molecules,ad Studied by Single Crystal ESR and ^1H-ENDOR Spectroscopies" Mol.Cryst.Liq.Cryst.

    • Related Report
      1992 Annual Research Report
  • [Publications] K.Furukawa: "Molecular Design,Synthesis,and Electron Spin Resonance Detection of a Ground-State Tridecet (S=6) Hydrocarbon as a Model for 2D Organic Ferro-and Superpara-Magnets" Mol.Cryst.Liq.Cryst.

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Teki: "Magnetic Behavior of (N-arylthio)-2,4,6-triphenylanilino Radical Crystals" Mol.Cryst.Liq.Cryst.

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Miura: "Syntheses of Nitroxide Polyradicals by the Catalytic Polycondensation of 3,5-Diethynylbenzenes Carrying Nitroxide Radicals with Diiodobenzenes and Their Magnetic Characterization" Mol.Cryst.Liq.Cryst.

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Teki: "Novel Organic Ions of High-Spin States" Mol.Cryst.Liq.Cryst.

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Takui: "Unusually Large Negative Spin Polarization of Hetero-Spin Composite High-Spin Carbenes as Models for Pureyl Organic Ferrimagnets: Topological Through-Bond Approaches and ESR/ENDOR Characterization" Mol.Cryst.Liq.Cryst.

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Matsushita: "Novel Organic Ions of High-Spin States 3.: ESR and ^1H-ENDOR Studies of a Monocation of m-phenylenebis(phenylmethylene)" Bull.Chem.Soc.Jpn.

    • Related Report
      1992 Annual Research Report
  • [Publications] 工位 武治: "有機磁性体" 材料科学. 28. 315-323 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Miura: "Molecular Design,Synthesis and Magnetic Chiacteugation of poly(phemylacetylene) with piーToporegucated Pendant Nctoomyl Raditals as Modelstus Aganic Superpuaーand Ferromagnets" J.Pol.Sci.

    • Related Report
      1991 Annual Research Report
  • [Publications] M.Matsushita: "Novel Organic Ions of HighーSpin States II.: Determenation of the Spin Multiplicitiy of the Ground State and HーENDOR Study of the Monoarion of mーPhenylenebis cphyeny Lmethylenel" J.Am.Chem.Soc.

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Teki: "Topology and spin Alignment in a Novel Orgamic HighーSpin Molecule,Bipheny(ー3,4'ーbiscphenylmethylene),as Stadied by ESR and a Generalozed UHF Hubbord Calculation" J.Am.Chem.Soc.

    • Related Report
      1991 Annual Research Report
  • [Publications] K.Furkawa: "Molecular Design,Synthesis,and Electron Spin Resonance Detection of a tridecet(S=6) HighーSpin Coufene Oligomes as models to 2ーD Organic Ferrsーand superparaーmagnets" J.Am.Chem.Soc.

    • Related Report
      1991 Annual Research Report
  • [Publications] H.Sakamoto: "Simultaneous Amplitude Measurement of TwoーRadioーFlezuoncy Fields in ElectronーNuclearーNuclear Triple Resonance" J.Mag Reson.

    • Related Report
      1991 Annual Research Report
  • [Publications] 伊藤 公一: "Molecular Magnetic Coupleing" Kluwer Academic Pubbisher, 437 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 岡本 昌幸: "Spin Density Distribution of an Organic HighーSpin Molecule,Biphenylー3,3'ーbisー(phenylmethylene),as Studied by ^1HーENDOR and a UHF Hubbard Calculation" Chemical Physics Letters. 173. 265-270 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 松下 道雄: "Novel Organic Ions of HighーSpin States;ESR Detection of the Radical Anion of mーphenylenebis(phenylmethylene)" Journal of American Chemical Society. 112. 4700-4703 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 藤田 郁夫: "Design,Preparation,and ESR Detection of a GroundーState Undecet(S=5)Hydrocarbon" Journal of American Chemical Society. 112. 4074-4075 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 伊藤 公一: "Role of Topology in Spin Alignment of Organic Materials" Advanced Organic Solid State Materials. 173. 51-62 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 工位 武治: "Role of HighーSpin Molecules as Models for Organic Ferroー and FerriーMagnets,and piーToporegulated Magnetic Polymers" Advanced Organic Solid State Materials. 173. 63-69 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 三浦 洋三: "Molecular Design Synthesis,and Magnetic Characterization of Poly(phe^^´nylacetyle^^´ne)with piーToporegulated Dangling Nitronyl Nitroxide Radicals as Models for Organic Superpara and FerroーMagnets" Maklomolekule Chemi.

    • Related Report
      1990 Annual Research Report
  • [Publications] 工位 武治: "有機磁性体ーその応用的可能性" ポリファイル. 27(5号). 39-45 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 明石 康一: "Role of Hyperconjugation in Aligning Spins in Organic Chemistry" Journal of American Chemical Society.

    • Related Report
      1990 Annual Research Report
  • [Publications] 八木 宏文: "Role of a Hetero Atom Bridge in Designing and Constructing HigherーDimensional HighーSpin Assemblies:Superexchange Interaction" Chemical Physics Letters.

    • Related Report
      1990 Annual Research Report
  • [Publications] 手木 芳男: "Intramolecular Spin Alignment in Organic HighーSpin Mclecules via an OxygenーAtom Bridge.A Heisenberg Hamiltonian Approach II." Chemical Physics Letters.

    • Related Report
      1990 Annual Research Report
  • [Publications] 阪本 博一: "Simultaneous Smpliluke Measurement of Two RadioーFrequency Fields in ElectronーNuclearーNuclear Triple Resonance" Joarnal of Magnetic Resonance.

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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