1996 年度実績報告書

パルスESR/ENDORによる安定ニトレン系高スピン有機分子の電子状態の研究

研究課題

研究課題/領域番号	08740462
研究機関	大阪市立大学
研究代表者	佐藤和信大阪市立大学, 理学部, 助手 (90264796)
キーワード	電子スピン共鳴 / 高スピン有機分子 / 高スピンニトレン / 五重項分子 / 微細構造
研究概要	ニトレン系高スピン有機分子である基底五重項分子1,3-ジニトレノ-5-ニトロベンゼン(1,3-DNB)及び七重項分子1,3,5-トリニトレノトリアジン(1,3,5-TNATA)のESR測定を行うことにより、ニトレンスピンサイトならびに分子内における複数のニトレンサイト間の磁気的双極子相互作用の研究を行った。測定試料には、それぞれのアジド前駆体を反磁性物質中に希釈した混晶単結晶及び無秩序配向試料を用いた。ESRの測定は、ヘリウムガス流量/圧力コントローラー(購入備品)を取り込んだヘリウムガスフロー式温度制御システムをオックスフォード社製温度可変コントローラーにより精密に制御しながら、ブルカ-社製ESP300ESR装置を使用して行った。 1,3,5-TNTAのESR測定より、七重項状態と思われるスペクトルを観測し、ベンゼン環と異なるヘテロ原子を含むπ共役系においてもスピンの分極機構が有効に働いていることを示した。 1,3-DNB分子については、観測されたESRスペクトルの解析から五重項状態における微細構造定数を決定し、微細構造定数は各々のニトレンサイト上で一中心スピン-スピン相互作用が支配的であると仮定した弱い相互作用モデルでほぼ完全に説明できることを明らかにした。そして、これまでに報告されてきた全ての五重項ビスニトレン分子の微細構造定数が2割以上過小に評価されていたことと誤りの原因となった解析上の不備を指摘し、電子構造/分子構造とよく整合する微細構造定数を決定した。π共役系にヘテロ原子を含む場合でも、π系におけるスピン分極機構が支配的に作用し、1,3-DNBの基底五重項状態の形成に寄与していることを明らかにした。

研究成果
(20件)

すべてその他

すべて文献書誌 (20件)

[文献書誌] 福澤明: "Electronic and molecular structures of quintet bisnitrene as studied by fine-structure ESR spectra from random orientation : Are the documented zfs constants correct?" Molecular Crystals and Liquid Crystals. 278. 253-260 (1996)
[文献書誌] 佐藤和信: "An FT-pulsed ESR/electron spin transient nutation study of hyperbranched π-aryl stable triplet and quartet molecules" Molecular Crystals and Liquid Crystals. 278. 295-300 (1996)
[文献書誌] 中澤重顕: "Electronic and molecular structures of 1, 3, 5-tris-(phenylmethyloene) benzene (S=3) as models for discotic high-spin liquid crystals ; Single crystal ESR and X-ray diffraction studies" Molecular Crystals and Liquid Crystals. 278. 261-269 (1996)
[文献書誌] 塩見大輔: "One-dimensional ferrimagnetic behavior of a hetero-spin chain in an organic radical crystal as probed by susceptibility and relaxation time neasurements" Molecular Crystals and Liquid Crystals. 278. 279-294 (1996)
[文献書誌] 工位武治: "FT pulsed ESR/ESTN (Electron Spin Transient Nutation) spectroscopy applied to high-spin systems" Molecular Crystals and Liquid Crystals. 279. 155-176 (1996)
[文献書誌] Jae-Young Bae: "Crystal structure and magnetic characterization of a building block for one-dimensional heterobimetallic polymeric complexes bridged by 2, 2'-bibenzimidazolate ligands" Molecular Crystals and Liquid Crystals. 286. 35-40 (1996)
[文献書誌] 佐藤和信: "Exact analytical solution of eigenfields and eigenenergies for high spins" Bulletin of Magnetic Resonance. 18. 173-174 (1996)
[文献書誌] 佐藤和信: "A powder-pattern ESR study of the quartet states of the precursors of a square-pyramidal Nitridochromium (V) complex, Cr (III) (bpb) Cl (H_2O) and Cr (III) (bpb) (N_3)_2" Bulletin of Magnetic Resonance. 18. 171-172 (1996)
[文献書誌] 佐藤和信: "A FT pulsed ESR/electron spin transient nutation study of the quartet state of Cr (III) in MgO powder : Detection of its apparently canishing ZFS" Bulletin of Magnetic Resonance. 18. 169-170 (1996)
[文献書誌] 塩見大輔: "FT pulsed ESR of exhange-coupled spin systems in transition metal clusters and low-dimensional magnets" Bulletin of Magnetic Resonance. 18. 155-156 (1996)
[文献書誌] 工位武治: "FT pulsed ESR/ESTN (electron spin transient nutation) spectroscopy applied to high-spin systems ; Direct evidence of the first high-spin polymer as models for organic ferro- and superpara-megnets" Bulletin of Magnetic Resonance. 18. 21-29 (1996)
[文献書誌] Andrew S. Ichimura: "Ferric iron porphyrin as studied by single-crystal cw and FT pulsed ESR/ESTN (electron spin transient nutation) spectroscopy" Bulletin of Magnetic Resonance. 18. 167-168 (1996)
[文献書誌] 中村敏浩: "Novel organic ions of high-spin states. 5. Generation of a high-spin ground-state anion from an intramoleculary spin-frastrated system" Journal of American Chemical Society. 118. 8684-8687 (1996)
[文献書誌] 矢野将文: "Synthesis of 1, 3-bis (diarylamino) benzenes as model precursors for one-dimensional organic ferromagnetic metals" Tetrahedron Letters. 37. 9207-9210 (1996)
[文献書誌] 塩見大輔: "A prerequisite for purely organic molecule-based ferrimagnetics : Breakdown of simple classical pictures" The Journal of Physical Chemistry. (印刷中). (1997)
[文献書誌] 工位武治: "Molecular design for polyionic organic ferromagnets and syntheses of model oligomers" Synthetic Metals. (印刷中). (1997)
[文献書誌] 佐藤和信: "Pulsed ESR/ENDOR and ESTN (electron spin transient nutation) study of polycationic high-spin states of one- and two-dimensional (diary lamino) benzenes" Synthetic Metals. (印刷中). (1997)
[文献書誌] 佐藤和信: "Polycationic high-spin states of one- and two-dimensional (diarylamino) benzenes as studied by pulsed ESR/electron spin transient nutation (ESTN) spectroscopy" MOlecular Crystals and Liquid Crystals. (印刷中). (1997)
[文献書誌] 工位武治: "O. Kahn (ed.), Magnetism : A Supramolecular Function" Kluwer Academic Publishers, 31 (1996)
[文献書誌] 工位武治: "M. M. turnbull, T. Sugimoto, L. K. Thompson (eds.), Molecule-based Magnetic Materials, Chapter 6" American Chemical Society, 18 (1996)

1996 年度 実績報告書

パルスESR/ENDORによる安定ニトレン系高スピン有機分子の電子状態の研究

研究代表者

佐藤 和信 大阪市立大学, 理学部, 助手 (90264796)

研究成果

[文献書誌] 福澤 明: "Electronic and molecular structures of quintet bisnitrene as studied by fine-structure ESR spectra from random orientation : Are the documented zfs constants correct?" Molecular Crystals and Liquid Crystals. 278. 253-260 (1996)

[文献書誌] 佐藤 和信: "An FT-pulsed ESR/electron spin transient nutation study of hyperbranched π-aryl stable triplet and quartet molecules" Molecular Crystals and Liquid Crystals. 278. 295-300 (1996)

[文献書誌] 中澤 重顕: "Electronic and molecular structures of 1, 3, 5-tris-(phenylmethyloene) benzene (S=3) as models for discotic high-spin liquid crystals ; Single crystal ESR and X-ray diffraction studies" Molecular Crystals and Liquid Crystals. 278. 261-269 (1996)

[文献書誌] 塩見 大輔: "One-dimensional ferrimagnetic behavior of a hetero-spin chain in an organic radical crystal as probed by susceptibility and relaxation time neasurements" Molecular Crystals and Liquid Crystals. 278. 279-294 (1996)

[文献書誌] 工位 武治: "FT pulsed ESR/ESTN (Electron Spin Transient Nutation) spectroscopy applied to high-spin systems" Molecular Crystals and Liquid Crystals. 279. 155-176 (1996)

[文献書誌] Jae-Young Bae: "Crystal structure and magnetic characterization of a building block for one-dimensional heterobimetallic polymeric complexes bridged by 2, 2'-bibenzimidazolate ligands" Molecular Crystals and Liquid Crystals. 286. 35-40 (1996)

[文献書誌] 佐藤 和信: "Exact analytical solution of eigenfields and eigenenergies for high spins" Bulletin of Magnetic Resonance. 18. 173-174 (1996)

[文献書誌] 佐藤 和信: "A powder-pattern ESR study of the quartet states of the precursors of a square-pyramidal Nitridochromium (V) complex, Cr (III) (bpb) Cl (H_2O) and Cr (III) (bpb) (N_3)_2" Bulletin of Magnetic Resonance. 18. 171-172 (1996)

[文献書誌] 佐藤 和信: "A FT pulsed ESR/electron spin transient nutation study of the quartet state of Cr (III) in MgO powder : Detection of its apparently canishing ZFS" Bulletin of Magnetic Resonance. 18. 169-170 (1996)

[文献書誌] 塩見 大輔: "FT pulsed ESR of exhange-coupled spin systems in transition metal clusters and low-dimensional magnets" Bulletin of Magnetic Resonance. 18. 155-156 (1996)

[文献書誌] 工位 武治: "FT pulsed ESR/ESTN (electron spin transient nutation) spectroscopy applied to high-spin systems ; Direct evidence of the first high-spin polymer as models for organic ferro- and superpara-megnets" Bulletin of Magnetic Resonance. 18. 21-29 (1996)

[文献書誌] Andrew S. Ichimura: "Ferric iron porphyrin as studied by single-crystal cw and FT pulsed ESR/ESTN (electron spin transient nutation) spectroscopy" Bulletin of Magnetic Resonance. 18. 167-168 (1996)

[文献書誌] 中村 敏浩: "Novel organic ions of high-spin states. 5. Generation of a high-spin ground-state anion from an intramoleculary spin-frastrated system" Journal of American Chemical Society. 118. 8684-8687 (1996)

[文献書誌] 矢野 将文: "Synthesis of 1, 3-bis (diarylamino) benzenes as model precursors for one-dimensional organic ferromagnetic metals" Tetrahedron Letters. 37. 9207-9210 (1996)

[文献書誌] 塩見 大輔: "A prerequisite for purely organic molecule-based ferrimagnetics : Breakdown of simple classical pictures" The Journal of Physical Chemistry. (印刷中). (1997)

[文献書誌] 工位 武治: "Molecular design for polyionic organic ferromagnets and syntheses of model oligomers" Synthetic Metals. (印刷中). (1997)

[文献書誌] 佐藤 和信: "Pulsed ESR/ENDOR and ESTN (electron spin transient nutation) study of polycationic high-spin states of one- and two-dimensional (diary lamino) benzenes" Synthetic Metals. (印刷中). (1997)

[文献書誌] 佐藤 和信: "Polycationic high-spin states of one- and two-dimensional (diarylamino) benzenes as studied by pulsed ESR/electron spin transient nutation (ESTN) spectroscopy" MOlecular Crystals and Liquid Crystals. (印刷中). (1997)

[文献書誌] 工位 武治: "O. Kahn (ed.), Magnetism : A Supramolecular Function" Kluwer Academic Publishers, 31 (1996)

[文献書誌] 工位 武治: "M. M. turnbull, T. Sugimoto, L. K. Thompson (eds.), Molecule-based Magnetic Materials, Chapter 6" American Chemical Society, 18 (1996)

1996 年度実績報告書

佐藤和信大阪市立大学, 理学部, 助手 (90264796)

[文献書誌] 福澤明: "Electronic and molecular structures of quintet bisnitrene as studied by fine-structure ESR spectra from random orientation : Are the documented zfs constants correct?" Molecular Crystals and Liquid Crystals. 278. 253-260 (1996)

[文献書誌] 佐藤和信: "An FT-pulsed ESR/electron spin transient nutation study of hyperbranched π-aryl stable triplet and quartet molecules" Molecular Crystals and Liquid Crystals. 278. 295-300 (1996)

[文献書誌] 中澤重顕: "Electronic and molecular structures of 1, 3, 5-tris-(phenylmethyloene) benzene (S=3) as models for discotic high-spin liquid crystals ; Single crystal ESR and X-ray diffraction studies" Molecular Crystals and Liquid Crystals. 278. 261-269 (1996)

[文献書誌] 塩見大輔: "One-dimensional ferrimagnetic behavior of a hetero-spin chain in an organic radical crystal as probed by susceptibility and relaxation time neasurements" Molecular Crystals and Liquid Crystals. 278. 279-294 (1996)

[文献書誌] 工位武治: "FT pulsed ESR/ESTN (Electron Spin Transient Nutation) spectroscopy applied to high-spin systems" Molecular Crystals and Liquid Crystals. 279. 155-176 (1996)

[文献書誌] 佐藤和信: "Exact analytical solution of eigenfields and eigenenergies for high spins" Bulletin of Magnetic Resonance. 18. 173-174 (1996)

[文献書誌] 佐藤和信: "A powder-pattern ESR study of the quartet states of the precursors of a square-pyramidal Nitridochromium (V) complex, Cr (III) (bpb) Cl (H_2O) and Cr (III) (bpb) (N_3)_2" Bulletin of Magnetic Resonance. 18. 171-172 (1996)

[文献書誌] 佐藤和信: "A FT pulsed ESR/electron spin transient nutation study of the quartet state of Cr (III) in MgO powder : Detection of its apparently canishing ZFS" Bulletin of Magnetic Resonance. 18. 169-170 (1996)

[文献書誌] 塩見大輔: "FT pulsed ESR of exhange-coupled spin systems in transition metal clusters and low-dimensional magnets" Bulletin of Magnetic Resonance. 18. 155-156 (1996)

[文献書誌] 工位武治: "FT pulsed ESR/ESTN (electron spin transient nutation) spectroscopy applied to high-spin systems ; Direct evidence of the first high-spin polymer as models for organic ferro- and superpara-megnets" Bulletin of Magnetic Resonance. 18. 21-29 (1996)

[文献書誌] 中村敏浩: "Novel organic ions of high-spin states. 5. Generation of a high-spin ground-state anion from an intramoleculary spin-frastrated system" Journal of American Chemical Society. 118. 8684-8687 (1996)

[文献書誌] 矢野将文: "Synthesis of 1, 3-bis (diarylamino) benzenes as model precursors for one-dimensional organic ferromagnetic metals" Tetrahedron Letters. 37. 9207-9210 (1996)

[文献書誌] 塩見大輔: "A prerequisite for purely organic molecule-based ferrimagnetics : Breakdown of simple classical pictures" The Journal of Physical Chemistry. (印刷中). (1997)

[文献書誌] 工位武治: "Molecular design for polyionic organic ferromagnets and syntheses of model oligomers" Synthetic Metals. (印刷中). (1997)

[文献書誌] 佐藤和信: "Pulsed ESR/ENDOR and ESTN (electron spin transient nutation) study of polycationic high-spin states of one- and two-dimensional (diary lamino) benzenes" Synthetic Metals. (印刷中). (1997)

[文献書誌] 佐藤和信: "Polycationic high-spin states of one- and two-dimensional (diarylamino) benzenes as studied by pulsed ESR/electron spin transient nutation (ESTN) spectroscopy" MOlecular Crystals and Liquid Crystals. (印刷中). (1997)

[文献書誌] 工位武治: "O. Kahn (ed.), Magnetism : A Supramolecular Function" Kluwer Academic Publishers, 31 (1996)

[文献書誌] 工位武治: "M. M. turnbull, T. Sugimoto, L. K. Thompson (eds.), Molecule-based Magnetic Materials, Chapter 6" American Chemical Society, 18 (1996)