2001 Fiscal Year Annual Research Report

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

Research Project

Project/Area Number	10304049
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)	塩見大輔大阪市立大学, 大学院・理学研究科, 助教授 (40260799) 佐藤和信大阪市立大学, 大学院・理学研究科, 講師 (90264796)
Keywords	分子磁性 / 有機磁性 / 分子スピークス / 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
Research Abstract	本年度も、新分子・物質開発においては当初の計画どおり、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モデル系の合成経路の開発を引き続き行った。本年度は、新たに水素結合集積型高スピン分子系を分子設計し、合成経路を開発をおこなった。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、C_<60>をベースとする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が、単離には至っていない。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、新規な環状中性高スピン系の設計・合成と2次元型超高スピンオリゴカルベン系のスピン同定を、パルスESR分光とベースとした遷移モーメント分光法の開発によっておこなった。本年度も引き続き、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、高スピン状態と低スピン状態間のコヒーレント共鳴的な量子スピントンネル現象を、ヤーン・テラー相互作用Assistedなスピンボトルネックに関連したものであることを昨年度に引き続き新たな理論的なアプローチに基づき証明した。その結果、アルカリ金属をドープしたCo_<60>結晶の超伝導機構を説明するヤーン・テラー理論に初めて実験的な証拠として提供した。C_<60>多価アニオン系ついては、新たに、2つのデキストリン分子をキャップした水溶性C_<60>系の多価アニオン系の高スピン状態を始めて検出し、C.Reedらの説への反駁を実験的に行った。C_<60>アニオン系、デカサイクレン多価アニオン系について、QバンドESR分光法による微細構造定数の絶対符号決定を試みた。

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-0 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 Oxophenalenoxyl : 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

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

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-0 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 Oxophenalenoxyl : 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)