1990 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, 助教授 (10117955)
Keywords	有機磁性 / 分子性磁性 / 有機フェリ磁性 / 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	1.研究目的我々はこれ迄に20年以上にわたって、反磁性を一般的磁気的特徴とする有機物質に強磁性やフェリ磁性的機能をもたせることを最終目的として,様々の有機高スピン分子を実際に設計・合成しそれらの実在を証明してきた。有機磁性研究もここ3,4年来強磁性的振舞を示す磁性高分子の報告によって多くの分野で注目を集め始めた。本研究では,有機磁の可能性を一層現実のものにするためには,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極めて重要であるとの視点に立って,有機フェリ磁性体モデル分子のスピン整列を電子一核多重共鳴法によって明らかにした。2.本年度の研究成果 (1)試料の作製典型的な有機フェリ磁性体モデル分子として基底三重項ジフェニルカルベン(T)と基底五重項メタフェニレンビス(フェニルメチレン)(Q)を4,4'位において酸素原子で架橋した4T4'Qーエ-テルを採用した。この分子はベンゼン環を5個もち,水素核の電子核二重共鳴( ^1HーENDOR)において帰属すべき水素核が多すぎるので,両端のベンゼン環を重水素化した4T4'Qーエ-テルd_8のトリスジアゾ前駆体を合成した。このジアゾ化合物をゲスト分子としてよく取り込むホスト単結晶としては重水素化ベンゾフェノンd_<10>を採用した。 (2) ^1HーENDOR測定と解析結果 4T4'Qーエ-テルd_8の生成は極低温下でトリスジアゾ前駆体の光分解によって得た。4T4'Qーエ-テルd_8の基底状態はスピン三重項であり,約10cm^<-1>上に近接五重項及び七重項をもつ。 ^1HーENDORスペクトルは基底三重項状態に対して観測された。12個の水素核に由来する信号がすべて観測され,超微細結合定数が負であるものが7個,正であるものが5個帰属された。従来の高スピン分子とは異なって,異常に大きな負のスピン分極が見い出され,4T4'Qーエ-テルは基底状態においてはTユニットがQユニットに対してスピン反転していることがわかった。

Research Products
(11 results)

All Other

All Publications (11 results)

[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)
[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)
[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)
[Publications] 伊藤公一: "Role of Topology in Spin Alignment of Organic Materials" Advanced Organic Solid State Materials. 173. 51-62 (1990)
[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)
[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.
[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)
[Publications] 明石康一: "Role of Hyperconjugation in Aligning Spins in Organic Chemistry" Journal of American Chemical Society.
[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.
[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.
[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.

1990 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] 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)

[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)

[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)

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

[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)

[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.

[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)

[Publications] 明石 康一: "Role of Hyperconjugation in Aligning Spins in Organic Chemistry" Journal of American Chemical Society.

[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.

[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.

[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.

伊藤公一大阪市立大学, 理学部, 教授 (70029403)

[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)

[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)

[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)

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

[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)

[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.

[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)

[Publications] 明石康一: "Role of Hyperconjugation in Aligning Spins in Organic Chemistry" Journal of American Chemical Society.

[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.

[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.

[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.