1999 年度実績報告書

分子スピニクスのための高磁場Wバンド量子位相FTパルス電子磁気共鳴法の開発

研究課題

研究課題/領域番号	10304049
研究機関	大阪市立大学
研究代表者	工位武治大阪市立大学, 理学部, 教授 (10117955)
研究分担者	塩見大輔大阪市立大学, 理学部, 助教授 (40260799) 佐藤和信大阪市立大学, 理学部, 講師 (90264796)
キーワード	分子磁性 / 有機磁性 / 分子スピニクス / 高磁場ESR / パルスESR / 量子位相 / Wバンド電子磁気共鳴 / スピン波
研究概要	2年度は、新分子・物質開発においては、これまでに我々が見出してきた強スピン分極型安定高スピン有機分子系を骨格とし、自己集積化の部位をもつ液晶モデル系の合成経路の開発を引き続き行った。また、これまでにモノアニオンラジカル結晶化に成功した例が2報なされているが、それらの手法を修飾し、新規な多価アニオン高スピン有機分子系クラスターの結晶化の試みを引き続き行った。磁気的な希釈系をガス・固体反応によって生成できる可能性があるので、C_<60>系結晶の手法を修飾してポリケトン系や平面性の高い高対称分子構造をもつ系について試みたが、目下のところ成功していない。ヘテロ原子核を拡張π共役系にもつ新規な多価カチオン高スピン基底状態系の合成に成功した。2年度は新たに、今なお論争中のC_<60>多価アニオンの高スピン状態の生成と基底状態の実験的な帰属をFT電子スピンニューテーション分光法によって行い、論争に決着をつけた。高スピン状態と低スピン状態のエネルギーギャップを実験的に決定し、両状態間の転換を初めて見いだしこの転換過程がヤーン・テラー相互作用Assistedなものであることを証明した。 CW及びパルス高周波・高磁場Wバンド電子スピン共鳴装置の立ち上げ作業の一部として、6Tの超伝導マグネット(ヘルムホルツ型)のセットアップとmK領域の測定を可能にする冷却部の設計を行った。2年度も高周波数化のための中間周波数(10GHz)の組み込みは、検出感度の点から重要な作業であるので平行して行った。引き続き、高周波・高磁場下での高スピン分子系におけるスピン系の液相系ダイナミクス・緩和過程の理論的な解析と予想を先行させて、スピンフラストレーション系を含む有機および無機系高スピン系の高周波・高磁場電子スピン共鳴分光の確立を理論と実験の両面から検討を続けた。人工磁性格子系に固有の巨大磁気双極子由来のスピン波は、新しい物質スピン波であるだけでなく、スピニクスデバイスの基本原形の一つであるので、強磁性共鳴の低温下マイクロ波平行励起実験を行い、磁気双極子スピン波のみが選択的に励起される現象を見いだした。これを説明するために、目下理論的解析を進めている。

研究成果

(29件)

すべてその他

すべて文献書誌 (29件)

[文献書誌] Jae Young Bae: "Random Orientation ESR Studies of Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation"Bulletin of Magnetic Resonance. 19. 39-43 (1999)
[文献書誌] K.Gotoh: "A Stable Neutral Hydrocarbon Radical : Synthesis, Crystal Structure and Physical Properties of 2,5,8-Tri-tert-butyl-phenalenyl"J.Am.Chem.Soc.. 121. 1619-1620 (1999)
[文献書誌] Shigeaki Nakazawa: "Electronic States and Spin Characterization of Polyanionic High-Spin Molecules and Clusters Derived from 1,3-Dibenzoylbenzene Derivatives as Studied by ESR/Electron Spin Transient Nutation Spectroscopy"Mol.Cryst. and Liq.Cryst.. 334. 11-21 (1999)
[文献書誌] Kozo Fukui: "Electronic Structure of a Stable Phenalenyl Radical as Studied by ESR/ENDOR, Paramagnetic NMR Spectroscopy and SQUID Measurements"Mol.Cryst. and Liq.Cryst.. 334. 49-58 (1999)
[文献書誌] Jae Young Bae: "Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation; Invalidity of Simple Extension of "π-Topdogy Rule" for Homoatomic Systems"Mol. Cryst. and Liq. Cryst.. 334. 59-68 (1999)
[文献書誌] Kazunobu Sato: "2D-Electron Spin Transient Nutation(2D-ESTN) Study of Stable High-Spin Carbene (S=3)"Mol.Cryst. and Liq.Cryst.. 334. 81-88 (1999)
[文献書誌] Daisuke Shiomi: "Charged Nitronyl Nitroxide Biradicals as Building Blocks for Molecular Ferrimagnetics"Mol. Cryst. and Liq. Cryst.. 334. 99-108 (1999)
[文献書誌] Daisuke Shiomi: "Possible Superhigh-Spin Cluster in the Crystals of a Novel Nitronyl Nitroxide Radical as Studied by FT Pulsed ESR"Mol.Cryst. and Liq.Cryst.. 335. 359-369 (1999)
[文献書誌] Ko Furukawa: "A Novel Spin Wave from Low-Dimensional Superlattice of Microstructured Ferromagnetic Thin Films"Mol.Cryst. and Liq.Cryst.. 335. 163-172 (1999)
[文献書誌] K.Fukui: "Electronic Structure of a Stable Phenalenyl Radical in Crystalline State as Studied by SQUID Measurements, cw-ESR, and ^<13>C CP/MAS NMR Spectroscopy"Synthetic Metals. 103. 2257-2258 (1999)
[文献書誌] M.C.B.L.Shohoji: "Polynionic High-Spin Hydrocarbons with High Symmetry"Synthetic Metals. 102. 1544-1545 (1999)
[文献書誌] K.Sato: "Persistent High-Spin Polycarbene (S=3) as Studied by 2D-ESTN Spectroscopy"Synthetic Metals. 103. 2269-2270 (1999)
[文献書誌] J.Y.Bae: "Spin Alignment in High-Spin Carbenes of Heteroatomic"Synthetic Metals. 103. 2261-2262 (1999)
[文献書誌] T.Nakai: "ESR Study of High-Spin Nitrenes with s-Triazine Skeleton"Synthetic Metals. 103. 2265-2266 (1999)
[文献書誌] K.Okada: "Structure and Photolysis of the Dimer of 2,2-(m-Phenylene)bis-(4,5-Diphenylmidazole-2-yl)Diradical"Synthetic Metals. 103. 2308-2309 (1999)
[文献書誌] D.Shiomi: "Magnetic Coupling of Nitronyl Nitroxide-Based Biradical Salts"Synthetic Metals. 103. 2271-2272 (1999)
[文献書誌] Masahiro Nishizawa: "Evidence for the Breakdown of Simple Classical Pictures of Organic Molecule-Based Ferrimagnetics:Low-Temperature Crystal Structure and Single-Crystal ESR Studies of an Organic Heterospin System"J.Phys.Chem.B. 104. 503-509 (2000)
[文献書誌] Daisuke Shiomi: "Spin-Spin Correlation function and Magnetic Susceptibility of Quantum Ferrimagnetic Spin Chains as models for Organic Molecule-Based Ferrimagnetics"J.Phys.Chem.B. 104. 1961-1965 (2000)
[文献書誌] M.Candida B. L.Shihoji: "Electronic and Molecular Structures of Polyanionic C_<60> Fullerene and High-Spin C_<60>^<n-> Clusters Studied by ESR/2D-Electron Spin Transient Nutation Spectroscopy"J.Am.Institute of Phys.. (in press). (2000)
[文献書誌] Kazunobu Sato: "A Stable High-Spin Polycarbene (S=3) as Studied by 2D-Electron Spin Transient Nutation Spectroscopy"J.Am.Institute of Phys.. (in press). (2000)
[文献書誌] Takeji Takui: "Two-Dimensional FT-Pulsed Electron Spin Transient Nutation Spectroscopy"J.Am.Institute of Phys.. (in press). (2000)
[文献書誌] K.Kamiyama: "Benzoic Acid and Phenol Derivatives of Nitronyl Nitroxide Biradical as Building Blocks of Organic Molecule-Based Ferrimagnetics"Applied Magnetic Resonance. (in press). (2000)
[文献書誌] M.Candida B. L.Shohoji: "Electronic Quartet and Triplet States of Polynionic C_<60> Fullerrene and Their Anomalous Spin Relaxation as Studied by cw-ESR/2D-Electron Spin Transient Nutation Spectroscopy"J.Am.Chem.Soc.. 122(in press). (2000)
[文献書誌] Yasushi Morita: "New Persistent Radicals: Synthesis and Electronic Spin Structure of 2,5,-Di-t-Butyl-6-Oxophenalenoxyl Derivatives"J.Am.Chem.Soc.. (in press). (2000)
[文献書誌] Akira Izuoka: "Spin Alignment in Singly Oxidized Spin-Polarized Diradical Donor: Thianthrene bis(nitronyl nitroxide)"J.Am.Chem.Soc.. (in press). (2000)
[文献書誌] J.Y.Bae: "Randomly Orientation ESR Studies of Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation; Eigenfield Analysis for High Spins and Off-principal-Axis Extra Lines"Applied Magnetic Resonance. (in press). (2000)
[文献書誌] 工位武治: "化学の世界記録"化学同人. 580 (1999)
[文献書誌] Takeji Takui: "Magnetic Properties of Organic Materials"Marcel Dekker, Inc.. 590 (1999)
[文献書誌] Takeji Takui: "Molecular Magnetism"Kodansya Publisher (in press). (2000)

1999 年度 実績報告書

分子スピニクスのための高磁場Wバンド量子位相FTパルス電子磁気共鳴法の開発

研究代表者

工位 武治 大阪市立大学, 理学部, 教授 (10117955)

研究成果

[文献書誌] Jae Young Bae: "Random Orientation ESR Studies of Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation"Bulletin of Magnetic Resonance. 19. 39-43 (1999)

[文献書誌] K.Gotoh: "A Stable Neutral Hydrocarbon Radical : Synthesis, Crystal Structure and Physical Properties of 2,5,8-Tri-tert-butyl-phenalenyl"J.Am.Chem.Soc.. 121. 1619-1620 (1999)

[文献書誌] Shigeaki Nakazawa: "Electronic States and Spin Characterization of Polyanionic High-Spin Molecules and Clusters Derived from 1,3-Dibenzoylbenzene Derivatives as Studied by ESR/Electron Spin Transient Nutation Spectroscopy"Mol.Cryst. and Liq.Cryst.. 334. 11-21 (1999)

[文献書誌] Kozo Fukui: "Electronic Structure of a Stable Phenalenyl Radical as Studied by ESR/ENDOR, Paramagnetic NMR Spectroscopy and SQUID Measurements"Mol.Cryst. and Liq.Cryst.. 334. 49-58 (1999)

[文献書誌] Jae Young Bae: "Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation; Invalidity of Simple Extension of "π-Topdogy Rule" for Homoatomic Systems"Mol. Cryst. and Liq. Cryst.. 334. 59-68 (1999)

[文献書誌] Kazunobu Sato: "2D-Electron Spin Transient Nutation(2D-ESTN) Study of Stable High-Spin Carbene (S=3)"Mol.Cryst. and Liq.Cryst.. 334. 81-88 (1999)

[文献書誌] Daisuke Shiomi: "Charged Nitronyl Nitroxide Biradicals as Building Blocks for Molecular Ferrimagnetics"Mol. Cryst. and Liq. Cryst.. 334. 99-108 (1999)

[文献書誌] Daisuke Shiomi: "Possible Superhigh-Spin Cluster in the Crystals of a Novel Nitronyl Nitroxide Radical as Studied by FT Pulsed ESR"Mol.Cryst. and Liq.Cryst.. 335. 359-369 (1999)

[文献書誌] Ko Furukawa: "A Novel Spin Wave from Low-Dimensional Superlattice of Microstructured Ferromagnetic Thin Films"Mol.Cryst. and Liq.Cryst.. 335. 163-172 (1999)

[文献書誌] K.Fukui: "Electronic Structure of a Stable Phenalenyl Radical in Crystalline State as Studied by SQUID Measurements, cw-ESR, and ^<13>C CP/MAS NMR Spectroscopy"Synthetic Metals. 103. 2257-2258 (1999)

[文献書誌] M.C.B.L.Shohoji: "Polynionic High-Spin Hydrocarbons with High Symmetry"Synthetic Metals. 102. 1544-1545 (1999)

[文献書誌] K.Sato: "Persistent High-Spin Polycarbene (S=3) as Studied by 2D-ESTN Spectroscopy"Synthetic Metals. 103. 2269-2270 (1999)

[文献書誌] J.Y.Bae: "Spin Alignment in High-Spin Carbenes of Heteroatomic"Synthetic Metals. 103. 2261-2262 (1999)

[文献書誌] T.Nakai: "ESR Study of High-Spin Nitrenes with s-Triazine Skeleton"Synthetic Metals. 103. 2265-2266 (1999)

[文献書誌] K.Okada: "Structure and Photolysis of the Dimer of 2,2-(m-Phenylene)bis-(4,5-Diphenylmidazole-2-yl)Diradical"Synthetic Metals. 103. 2308-2309 (1999)

[文献書誌] D.Shiomi: "Magnetic Coupling of Nitronyl Nitroxide-Based Biradical Salts"Synthetic Metals. 103. 2271-2272 (1999)

[文献書誌] Masahiro Nishizawa: "Evidence for the Breakdown of Simple Classical Pictures of Organic Molecule-Based Ferrimagnetics:Low-Temperature Crystal Structure and Single-Crystal ESR Studies of an Organic Heterospin System"J.Phys.Chem.B. 104. 503-509 (2000)

[文献書誌] Daisuke Shiomi: "Spin-Spin Correlation function and Magnetic Susceptibility of Quantum Ferrimagnetic Spin Chains as models for Organic Molecule-Based Ferrimagnetics"J.Phys.Chem.B. 104. 1961-1965 (2000)

[文献書誌] M.Candida B. L.Shihoji: "Electronic and Molecular Structures of Polyanionic C_<60> Fullerene and High-Spin C_<60>^<n-> Clusters Studied by ESR/2D-Electron Spin Transient Nutation Spectroscopy"J.Am.Institute of Phys.. (in press). (2000)

[文献書誌] Kazunobu Sato: "A Stable High-Spin Polycarbene (S=3) as Studied by 2D-Electron Spin Transient Nutation Spectroscopy"J.Am.Institute of Phys.. (in press). (2000)

[文献書誌] Takeji Takui: "Two-Dimensional FT-Pulsed Electron Spin Transient Nutation Spectroscopy"J.Am.Institute of Phys.. (in press). (2000)

[文献書誌] K.Kamiyama: "Benzoic Acid and Phenol Derivatives of Nitronyl Nitroxide Biradical as Building Blocks of Organic Molecule-Based Ferrimagnetics"Applied Magnetic Resonance. (in press). (2000)

[文献書誌] M.Candida B. L.Shohoji: "Electronic Quartet and Triplet States of Polynionic C_<60> Fullerrene and Their Anomalous Spin Relaxation as Studied by cw-ESR/2D-Electron Spin Transient Nutation Spectroscopy"J.Am.Chem.Soc.. 122(in press). (2000)

[文献書誌] Yasushi Morita: "New Persistent Radicals: Synthesis and Electronic Spin Structure of 2,5,-Di-t-Butyl-6-Oxophenalenoxyl Derivatives"J.Am.Chem.Soc.. (in press). (2000)

[文献書誌] Akira Izuoka: "Spin Alignment in Singly Oxidized Spin-Polarized Diradical Donor: Thianthrene bis(nitronyl nitroxide)"J.Am.Chem.Soc.. (in press). (2000)

[文献書誌] J.Y.Bae: "Randomly Orientation ESR Studies of Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation; Eigenfield Analysis for High Spins and Off-principal-Axis Extra Lines"Applied Magnetic Resonance. (in press). (2000)

[文献書誌] 工位武治: "化学の世界記録"化学同人. 580 (1999)

[文献書誌] Takeji Takui: "Magnetic Properties of Organic Materials"Marcel Dekker, Inc.. 590 (1999)

[文献書誌] Takeji Takui: "Molecular Magnetism"Kodansya Publisher (in press). (2000)

1999 年度実績報告書

工位武治大阪市立大学, 理学部, 教授 (10117955)