1999 Fiscal Year Annual Research Report

単分子有機磁石及びセミマクロ巨大スピン協同系の磁気双極子スピン波のスピニクス

Research Project

Project/Area Number	11224208
Research Institution	Osaka City University
Principal Investigator	工位武治大阪市立大学, 理学部, 教授 (10117955)
Co-Investigator(Kenkyū-buntansha)	佐藤和信大阪市立大学, 理学部, 講師 (90264796) 塩見大輔大阪市立大学, 理学部, 助教授 (40260799)
Keywords	単分子有機磁石 / セミマクロスピン系 / 磁気双極子スピン波 / スピニクス / 有機磁性 / 分子磁性 / ウォーカーモード / スピン波
Research Abstract	初年度はまず、群論的な考察をとりいれた新分子設計の指針に基づいてB-1単分子有機磁石(超常磁性体) (本研究(B))モデル分子系(S=2-6)として強スピン分極型の高スピン分子を、合成ルートを開発した。絶対値の大きな負の微細構造定数を持たせるために、軸対称2次元高対称性構造を骨格にもつ共役オリゴカルべン、ポリニトレン系と大きな非局在効果をもつ芳香環をトポロジー的に配置した系を合成した。実験的な困難さ(極低温でのスピントンネル効果の検出)を軽減するために、電子的基底状態において絶対値の大きな微細構造定数をもつ系の開発は重要である。また、 (B)では、有機分子固有の単分子磁石の性質を解明するために、分子内に弱いスピン間の交換相互作用をもつホモスピンあるいはへテロスピン系では微細構造テンソルに軸対称性がない場合でもB(静磁場)-assistedスピントンネル効果が現れることに注目した分子設計と合成を行った(B-2)。これらの系では、異なるスピン状態の副準位間に群論的なスピン混合が許される特徴がある。目下、物性的な測定の準備をしている。 (A)の研究対象としてのA-1セミマクロスケールで群論的な縮重機能をもつ2次元人工格子型薄膜パーマロイ強磁性体モデル系については、微小巨大スピン束を配列する群論的な対称性(周期性)と個々の束の形状の関連を磁気双極子スピン波の遷移強度に注目して解析した。方法論的には未知な部分が多いが、当面は緩和現象を考慮しない多体系擬スピンハミルトニアンアプローチを用いた。一方、(C)の課題では、すでに予備実験は終えているので初年度からパラメトリック励起実験をデュアルモード空洞共振器(Xバンド)(備品に計上)を用いて行った。本研究で得られるスピン波は、静磁場Bに対する異方性が極端に大きいので、タイムコンシューミングな実験となった。(実際の測定においては特定モードの非線形効果の理論的な予測は指針にならなかった)。人工格子系の熱浴の特性は、目下のところ全く未知なので、極低温に至る広範な温度領域での実験を行い、詳細な測定を現在なお実行中であるが、磁気双極子スピン波のみが選択的に励起される現象を初めて見いだした。今後、理論的な考察を行う予定である。

Research Products

(29 results)

All Other

All Publications (29 results)

[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] Kozo Fukui: "Electronic Structure of a Stable Phenalenyl Radical as Studied by ESR/ENDOR, Paramagnetic NMR Spectroscopy and SQUID Measurements"Mol. Cryst. and Liq. Crust.. 334. 49-58 (1999)
[Publications] Jae Young Bae: "Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation ; Invalidity of Simple Extersion of "π-Topology Rule" for Homoatomic Systems"Mol. Cryst. and Liq. Cryst.. 334. 59-68 (1999)
[Publications] Kazunobu Sato: "2D-Electron Spin Transient Nutation (2D-ESTN) Studu of Stable High-Spin Carbene (S=3)"Mol. Cryst. and Liq. Cryst.. 334. 81-88 (1999)
[Publications] Daisuke Shiomi: "Charged Nitronyl Nitroxide Biradicals as Building Blocks for Molecular Ferrimagnetics"Mol. Cryst. and Liq. Cryst.. 334. 99-108 (1999)
[Publications] Daisuke Shiom: "Possible Superhigh- Spin Cluster in the Crystals of a Novel Nitronyl Nitoxide Radical as Studied by FT Pulsed ESR"Mol. Cryst. and Liq. Cryst.. 335. 359-369 (1999)
[Publications] No Furukawa: "A Novel Spin Wave from Low-Dimensional Superlattice of Microstructured Ferromagnetic Thin Films"Mol. Cryst. and Liq. Cryst.. 335. 163-172 (1999)
[Publications] 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 Spectros copy"Synthetic Metals. 103. 2257-2258 (1999)
[Publications] M. C. B. L. Shohoji: "Polyanionic High-Spin Hydrocarbons with High Symmetry"Synthetic Metals. 102. 1544-1545 (1999)
[Publications] K. Sato: "Persistent High-Spin Polycarbene (S=3) as Studied by 2D-ESTN Spectroscopy"Synthetic Metals. 103. 2269-2270 (1999)
[Publications] J. Y. Bae: "Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation"Synthetic Metals. 103. 2261-2262 (1999)
[Publications] T. Nakai: "ESR Study of High-Spin Nitrenes with s-Triazine Skeleton"Synthetic Metals. 103. 2265-2266 (1999)
[Publications] 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)
[Publications] D. Shiomi: "Magnetic Coupling of Nitronyl Nitroxide-Based Biradical Salts"Synthetic Metals. 103. 2271-2272 (1999)
[Publications] 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)
[Publications] 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)
[Publications] M. Candida B. L. Shohoji: "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)
[Publications] Kazunobu Sato: "A Stable High-Spin Polycarbene (S=3) as Studies by 2D-Electron Spin Transient Nutation Spectroscopy"J. Am. Institute of Phys.. (in press). (2000)
[Publications] Takeji Takui: "Two-Dimensional FT-Pulsed Electron Spin Transient Nutation Spectroscopy"J. Am. Institute of Phys.. (in press). (2000)
[Publications] 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)
[Publications] M. Candida B. L. Shohoji: "Electrinic Quartet and Triplet States of Polyanionic C_<60>Fullerrene and Their Anomalous Spin Relaxation as Studied by cw-ESR/2D-Electron Spin Transient Nutaion Spectroscopy"J. Am. Chem. Soc.. 122(in press). (2000)
[Publications] 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)
[Publications] Akira Izuoka: "Spin Alignment in Single Oxidized Spin-Polarized Diradical Donor: Thianthrene bus (nitronyl nitroxide)"J. Am. Chem. Soc. (in press). (2000)
[Publications] J. Y. Bae: "Randomly Orientation ESR Studies of Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation ; Eigenfield And Ysis for High Spins and Off-Principal-Axis Extra Lines"Applied Magnetic Resonance. (in press). (2000)
[Publications] 工位武治: "化学の世界記録"化学同人. 580 (1999)
[Publications] Takeji Takui: "Magnetic Properties of Organic Materials"Marcel Dekker, Inc.. 590 (1999)
[Publications] Takeji Takui: "Molecular Magnetism"Kodansya Publisher (in press). (2000)

1999 Fiscal Year Annual Research Report

単分子有機磁石及びセミマクロ巨大スピン協同系の磁気双極子スピン波のスピニクス

Principal Investigator

工位 武治 大阪市立大学, 理学部, 教授 (10117955)

Research Products

[Publications] 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)

[Publications] 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)

[Publications] 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)

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

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

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

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

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

[Publications] No Furukawa: "A Novel Spin Wave from Low-Dimensional Superlattice of Microstructured Ferromagnetic Thin Films"Mol. Cryst. and Liq. Cryst.. 335. 163-172 (1999)

[Publications] 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 Spectros copy"Synthetic Metals. 103. 2257-2258 (1999)

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

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

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

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

[Publications] 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)

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

[Publications] 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)

[Publications] 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)

[Publications] M. Candida B. L. Shohoji: "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)

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

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

[Publications] 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)

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

[Publications] 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)

[Publications] Akira Izuoka: "Spin Alignment in Single Oxidized Spin-Polarized Diradical Donor: Thianthrene bus (nitronyl nitroxide)"J. Am. Chem. Soc. (in press). (2000)

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

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

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

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

工位武治大阪市立大学, 理学部, 教授 (10117955)