1992 Fiscal Year Annual Research Report

有機フェリ磁性体モデル分子のスピン整列機構の電子一核二重及び三重共鳴による研究

Research Project

Project/Area Number	02453014
Research Institution	Osaka City University
Principal Investigator	伊藤公一大阪市立大学, 理学部, 教授 (70029403)
Co-Investigator(Kenkyū-buntansha)	工位武治大阪市立大学, 理学部, 教授 (10117955)
Keywords	有機フェリ磁性体 / 異常負スピン / 分子性有機磁性 / ENDOR / πトポロジー / 多重項間相互作用 / ヘテロスピン系 / スピン化学
Research Abstract	有機磁性の可能性を現実のものとするには、磁性高分子の磁性発現機構の解明と共に一方では強磁性的スピン整列以外の多様なスピン秩序状態を見い出すことが重要である。本研究では、有機フェリ磁性体のモデルヘテロスピン系をはじめて設計・合成し、基底スピン状態におけるスピン密度分布の全解折を行った。その結果、異常な大きさの負のスピンが実在し、これはヘテロスピンの一方が他方に対して反転していることに由来することが証明された。その結果、異常巨大スピンは、ヘテロスピン反強磁性系に固有の性質であり、分子性有機磁性体の分子設計上有用な物理的描像を提供することがわかった。またこれ迄の化学における負のスピンの概念を修正する必要があることを実験と理論の両面から明らかにした。典型的なフェリ磁性分子として基底三重項ジフェニルカルベンと基底五重項メタフェニレンビスフェニルメチレンを4、4′位において酸素原子で架橋した4T4′Qエーテルを採用した。現在迄に、エーテル基を狭む二つのベンゼン環を重水素化したシアゾ前駆体の合成には、予想に反して全く新しいルートの開発が必要であることがわかったので、水素核のENDORスペクトルの全解折には無重水素化前駆体を採用した。ベンゾフェノンd_<+10>中に磁気的に希釈した無重水素化4T4′Qエーテルの水素核のENDORスペクトルの完全解析の結果、二価炭素及び水素核をもたない炭素サイト以外のすべての炭素サイト上のπスピン密度を実験的に決定した。その結果、反転ヘテロスピン系のスピン密度は、スピンカップリングの群論的収縮のために古典的描像に対して小さくなることも実験的に明らかになった。フェリ磁性分子のスピン密度分布は、弱く相互作用した三重項ー五重項相互作用モデルによって定量的に説明できた。二価炭素は^<13>Cによる標識化のための合成は、近々終了するので、二価炭素上の巨大負スピンの実験的決定を行う予定である。

Research Products

(14 results)

All Other

All Publications (14 results)

[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)
[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)
[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.
[Publications] Y.Teki: "Topology and Spin Alignment in Organic High-Spin Molecules" Bull.Magn.Reson.
[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.
[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.
[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.
[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.
[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.
[Publications] Y.Teki: "Magnetic Behavior of (N-arylthio)-2,4,6-triphenylanilino Radical Crystals" Mol.Cryst.Liq.Cryst.
[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.
[Publications] Y.Teki: "Novel Organic Ions of High-Spin States" Mol.Cryst.Liq.Cryst.
[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.
[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.

1992 Fiscal Year Annual Research Report

有機フェリ磁性体モデル分子のスピン整列機構の電子一核二重及び三重共鳴による研究

Principal Investigator

伊藤 公一 大阪市立大学, 理学部, 教授 (70029403)

Research Products

[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)

[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)

[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.

[Publications] Y.Teki: "Topology and Spin Alignment in Organic High-Spin Molecules" Bull.Magn.Reson.

[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.

[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.

[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.

[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.

[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.

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

[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.

[Publications] Y.Teki: "Novel Organic Ions of High-Spin States" Mol.Cryst.Liq.Cryst.

[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.

[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.

伊藤公一大阪市立大学, 理学部, 教授 (70029403)