2001 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, 大学院・理学研究科, 教授 (10117955)
Co-Investigator(Kenkyū-buntansha)	佐藤和信大阪市立大学, 大学院・理学研究科, 講師 (90264796) 塩見大輔大阪市立大学, 大学院・理学研究科, 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	本年度も、本研究(B)として、群論的に高い対称性をもつ高スピン分子系の設計と合成を引き続き行い、単分子有機磁石(超常磁性体)モデル系となる強スピン分極構造をもつ化学的に安定な高スピン分子(S=3-6のオリゴカルベン系、およびオリゴニトレン系)を極低温下で発生し、CW ESR微細構造スペクトルの全解析によって、同定した。その結果、次元性を制御した水素結合型集積系高スピン分子クラスターの設計が可能であることが分かった。全解析においては、ハイブリッド型の厳密な数値的対角化に基づく固有磁場法をさらに改良し、分子構造とスピン構造が整合するスピンハミルトニアンパラメータが実験的に抽出することができた。分子構造の解析には、オリゴカルベンやニトレンのように一中心型のスピン間相互作用が比較的大きく寄与するスピン構造をもつ系では、S=1のスピンユニット間のスピン-スピン相互作用がどの程度微細構造定数と分子構造に影響を及ぼすかを理論的に詳細に検討し、相互作用の大きさと共役系の大きさとの相関を見いだした。本年度も引き続き、新しいスピニクス分子系として、スピン緩和がスローダウンするようなスピン環境系として、高い対称性をもつC_<60>多価アニオン系をとりあげた結果、新たに見いだした共鳴型のスピントンネル現象は、動的なヤーン・テラー効果を介してC_<60>由来の高温超伝導発現のメカニズムに直接深く関与していることを結論した。研究(A)では、強磁性体薄膜をミクロンオーダーで微細加工した擬一次元及び二次元超格子構造体において見いだした2種類の新たな量子スピン波モードの全解析を行った。一つは、lateral Walkerとも言うべきスピン波で、もう一つは、磁気双極子スピン波である。後者は、超格子の数に依存して出現し、セミマクロスコピックな量子現象である可能性を強く示唆した。マイクロ波の平行励起実験を行ったところ、弱いマイクロ波励起でも、極低温において、擬一次元磁気双極子スピン波モードのみが、非線形現象を示した。引き続き、この特異な現象の理論的な考察を行っている。

Research Products
(29 results)

All Other

All Publications (29 results)

[Publications] J.Inoue et al.: "The first detection of a Clar's hydrocarbon,2,6,10-tri-tert-butyltriangulene: A ground-state triplet of non-Kekule polynuclear benzenoid hydrocarbon"J.Am.Chem.Soc.. 123. 12702-12703 (2001)
[Publications] D.Shiomi et al.: "Single-component molecule-based ferrimagnetics"J.Am.Chem.Soc.. 123. 11823-11824 (2001)
[Publications] Y.Morita et al.: "6-oxophenalenoxyl derivatives covalently linked to TTF moieties:synthesis,ESR/ENDOR measurements,and DFT calculations"Tetrahedron Lett.. 42. 7991-7995 (2001)
[Publications] Y.Morita et al.: "New stable neutral radical with intramolecular hydrogen bonding: Synthesis and characterization of 2,5,8-tri-tert-butyl-7-hydroxy-6-oxophenalenoxyl"Org.Lett.. 3. 3099-3102 (2001)
[Publications] T.Kanaya et al.: "Single-component ferrimagnetics: triplet-doublet composite molecules as constituents of purely organic molecule-based ferrimagnets"Polyhedron. 20. 1397-1402 (2001)
[Publications] S.Hase et al.: "Magnetic properties of phenol-substituted nitronyl nitroxide biradicals as building blocks of organic salt ferrimagnets"Polyhedron. 20. 1403-1409 (2001)
[Publications] O.Nagao et al.: "Magnetic behavior of a manganese(II) complex of nitroxide-substituted 1,3-di(4-pyridyl)benzene"Polyhedron. 20. 1653-1658 (2001)
[Publications] H.Mori et al.: "Magnetic behavior of copper(II) complexes of a nitronyl-nitroxide-substituted pyrimidine"Polyhedron. 20. 1663-1668 (2001)
[Publications] T.Okamoto et al.: "Synthesis and properties of benzooxazinophenooxazine and the related compounds"Synth.Met.. 120. 933-934 (2001)
[Publications] S.Nakazawa et al.: "Electronic states of polyanionic high-spin C-60 fullerene and their clusters: anomalous spin relaxation and Jahn-Teller effects"Synth.Met.. 121. 1169-1170 (2001)
[Publications] K.Fukui et al.: "X-and W-band ESR study on gamma-cyclodextrin bicapped C-60 after NH3-gas doping"Synth.Met.. 121. 1171-1172 (2001)
[Publications] K.Fukui et al.: "Electronic spin structure of novel persistent neutral radical with 1,3-diazaphenalene skeleton as studied by electron-nuclear magnetic resonance spectroscopies"Synth.Met.. 121. 1770-1771 (2001)
[Publications] M.Sakai et al.: "Low-dimensional molecule-based magnets with hydrogen-bonded network"Synth.Met. 121. 1776-1777 (2001)
[Publications] S.Kanaya et al.: "Synthesis and properties of a new-type nitroxide radical with a bulky 2,4,6-triphenylphenyl substituent"Synth.Met. 121. 1808-1809 (2001)
[Publications] D.Shiomi et al.: "Molecular design of organic ferrimagnets"Synth.Met. 121. 1810-1811 (2001)
[Publications] K.Sato et al.: "Pulsed ESR/2D-electron spin transient nutation study of stable high-spin polycarbenes"Synth.Met.. 121. 1816-1817 (2001)
[Publications] K.Tanaka et al.: "Cw/pulsed ESR study of bis[dianthrylcarbene]coupled by 1,4-diethynylbenzene"Synth.Met.. 121. 1818-1819 (2001)
[Publications] T.Nishio et al.: "Ground-state high-spin iron(III)octaethylporphyrin as studied by single-crystal cw/pulsed ESR spectroscopy"Synth.Met.. 121. 1820-1821 (2001)
[Publications] H.Matsuoka et al.: "Transition moment spectroscopy-based simulation of 2D electron spin transient nutation spectra for high spin chemistry"Synth.Met.. 121. 1822-1823 (2001)
[Publications] K.Fukui et al.: "The first non-Kekule polynuclear aromatic high-spin hydrocarbon: Generation of a triangulene derivative and band structure calculation of triangulene-based high-spin hydrocarbons"Synth.Met.. 121. 1824-1825 (2001)
[Publications] N.Oda et al.: "Highly symmetric high-spin oligonitrenes; molecular design for super high-spin systems with robust pi-spin polarisation"Synth.Met.. 121. 1840-1841 (2001)
[Publications] D.Shiomi et al.: "Quantum ferrimagnetism based on organic biradicals with a spin-O ground state: Numerical calculations of molecule-based ferrimagnetic spin chains"J.Phys.Chem.B. 105. 2932-2938 (2001)
[Publications] S.Hase et al.: "2Phenol-substituted nitronyl nitroxide biradicals with a triplet(S=1)ground state"J.Mater.Chem. 11. 756-760 (2001)
[Publications] D.Shiomi et al.: "A Molecular Quantum Description of Spin Alignments in Molecule-Based Ferrimagnets:Numerical Calculations of Thermodynamic Properties"J.Phys.Chem.A. (印刷中).
[Publications] Y.Morita et al.: "New Stable Oxophenatenoxyl: Preparation and Characterization of a 4-Oxophenalenoxyl Derivative"Mol.Cryst.Liq.Cryst.. (印刷中).
[Publications] D.Shiomi et al.: "Organic Molecule-Based Ferrimagnetism as Studied by Numerical Calculations of a Model Hamiltonian"Mol.Cryst.Liq.Cryst.. (印刷中).
[Publications] K.Sato et al.: "Electronic and molecular structures of dendrimeric high-spin polycarbenes as studied by CW and pulsed ESR-based electron spin transient nutation spectroscopy"Mol.Cryst.Liq.Cryst.. (印刷中).
[Publications] K.Tanaka et al.: "Extremely π-delocalized nature of dianthrylcarbene-based high-spin systems as studied by CW and pulsed 2-D electron-spin transient nutation spectroscopy"Mol.Cryst.Liq.Cryst.. (印刷中).
[Publications] Y.Morita et al.: "Redox-Based Spin Diversity in a 6-Oxophenalenoxyl System: Generation,ESR/ENDOR/TRIPLE,and Theoretical Studies of the 2,5,8-Tri-tert-Butylphenalenyl-1,6-bis(olate)Salts"Org.Lett.. (印刷中).

2001 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, 大学院・理学研究科, 教授 (10117955)

Research Products

[Publications] J.Inoue et al.: "The first detection of a Clar's hydrocarbon,2,6,10-tri-tert-butyltriangulene: A ground-state triplet of non-Kekule polynuclear benzenoid hydrocarbon"J.Am.Chem.Soc.. 123. 12702-12703 (2001)

[Publications] D.Shiomi et al.: "Single-component molecule-based ferrimagnetics"J.Am.Chem.Soc.. 123. 11823-11824 (2001)

[Publications] Y.Morita et al.: "6-oxophenalenoxyl derivatives covalently linked to TTF moieties:synthesis,ESR/ENDOR measurements,and DFT calculations"Tetrahedron Lett.. 42. 7991-7995 (2001)

[Publications] Y.Morita et al.: "New stable neutral radical with intramolecular hydrogen bonding: Synthesis and characterization of 2,5,8-tri-tert-butyl-7-hydroxy-6-oxophenalenoxyl"Org.Lett.. 3. 3099-3102 (2001)

[Publications] T.Kanaya et al.: "Single-component ferrimagnetics: triplet-doublet composite molecules as constituents of purely organic molecule-based ferrimagnets"Polyhedron. 20. 1397-1402 (2001)

[Publications] S.Hase et al.: "Magnetic properties of phenol-substituted nitronyl nitroxide biradicals as building blocks of organic salt ferrimagnets"Polyhedron. 20. 1403-1409 (2001)

[Publications] O.Nagao et al.: "Magnetic behavior of a manganese(II) complex of nitroxide-substituted 1,3-di(4-pyridyl)benzene"Polyhedron. 20. 1653-1658 (2001)

[Publications] H.Mori et al.: "Magnetic behavior of copper(II) complexes of a nitronyl-nitroxide-substituted pyrimidine"Polyhedron. 20. 1663-1668 (2001)

[Publications] T.Okamoto et al.: "Synthesis and properties of benzooxazinophenooxazine and the related compounds"Synth.Met.. 120. 933-934 (2001)

[Publications] S.Nakazawa et al.: "Electronic states of polyanionic high-spin C-60 fullerene and their clusters: anomalous spin relaxation and Jahn-Teller effects"Synth.Met.. 121. 1169-1170 (2001)

[Publications] K.Fukui et al.: "X-and W-band ESR study on gamma-cyclodextrin bicapped C-60 after NH3-gas doping"Synth.Met.. 121. 1171-1172 (2001)

[Publications] K.Fukui et al.: "Electronic spin structure of novel persistent neutral radical with 1,3-diazaphenalene skeleton as studied by electron-nuclear magnetic resonance spectroscopies"Synth.Met.. 121. 1770-1771 (2001)

[Publications] M.Sakai et al.: "Low-dimensional molecule-based magnets with hydrogen-bonded network"Synth.Met. 121. 1776-1777 (2001)

[Publications] S.Kanaya et al.: "Synthesis and properties of a new-type nitroxide radical with a bulky 2,4,6-triphenylphenyl substituent"Synth.Met. 121. 1808-1809 (2001)

[Publications] D.Shiomi et al.: "Molecular design of organic ferrimagnets"Synth.Met. 121. 1810-1811 (2001)

[Publications] K.Sato et al.: "Pulsed ESR/2D-electron spin transient nutation study of stable high-spin polycarbenes"Synth.Met.. 121. 1816-1817 (2001)

[Publications] K.Tanaka et al.: "Cw/pulsed ESR study of bis[dianthrylcarbene]coupled by 1,4-diethynylbenzene"Synth.Met.. 121. 1818-1819 (2001)

[Publications] T.Nishio et al.: "Ground-state high-spin iron(III)octaethylporphyrin as studied by single-crystal cw/pulsed ESR spectroscopy"Synth.Met.. 121. 1820-1821 (2001)

[Publications] H.Matsuoka et al.: "Transition moment spectroscopy-based simulation of 2D electron spin transient nutation spectra for high spin chemistry"Synth.Met.. 121. 1822-1823 (2001)

[Publications] K.Fukui et al.: "The first non-Kekule polynuclear aromatic high-spin hydrocarbon: Generation of a triangulene derivative and band structure calculation of triangulene-based high-spin hydrocarbons"Synth.Met.. 121. 1824-1825 (2001)

[Publications] N.Oda et al.: "Highly symmetric high-spin oligonitrenes; molecular design for super high-spin systems with robust pi-spin polarisation"Synth.Met.. 121. 1840-1841 (2001)

[Publications] D.Shiomi et al.: "Quantum ferrimagnetism based on organic biradicals with a spin-O ground state: Numerical calculations of molecule-based ferrimagnetic spin chains"J.Phys.Chem.B. 105. 2932-2938 (2001)

[Publications] S.Hase et al.: "2Phenol-substituted nitronyl nitroxide biradicals with a triplet(S=1)ground state"J.Mater.Chem. 11. 756-760 (2001)

[Publications] D.Shiomi et al.: "A Molecular Quantum Description of Spin Alignments in Molecule-Based Ferrimagnets:Numerical Calculations of Thermodynamic Properties"J.Phys.Chem.A. (印刷中).

[Publications] Y.Morita et al.: "New Stable Oxophenatenoxyl: Preparation and Characterization of a 4-Oxophenalenoxyl Derivative"Mol.Cryst.Liq.Cryst.. (印刷中).

[Publications] D.Shiomi et al.: "Organic Molecule-Based Ferrimagnetism as Studied by Numerical Calculations of a Model Hamiltonian"Mol.Cryst.Liq.Cryst.. (印刷中).

[Publications] K.Sato et al.: "Electronic and molecular structures of dendrimeric high-spin polycarbenes as studied by CW and pulsed ESR-based electron spin transient nutation spectroscopy"Mol.Cryst.Liq.Cryst.. (印刷中).

[Publications] K.Tanaka et al.: "Extremely π-delocalized nature of dianthrylcarbene-based high-spin systems as studied by CW and pulsed 2-D electron-spin transient nutation spectroscopy"Mol.Cryst.Liq.Cryst.. (印刷中).

[Publications] Y.Morita et al.: "Redox-Based Spin Diversity in a 6-Oxophenalenoxyl System: Generation,ESR/ENDOR/TRIPLE,and Theoretical Studies of the 2,5,8-Tri-tert-Butylphenalenyl-1,6-bis(olate)Salts"Org.Lett.. (印刷中).

工位武治大阪市立大学, 大学院・理学研究科, 教授 (10117955)