2001 Fiscal Year Annual Research Report

パルス電子スピン共鳴分光法による高対称高スピン有機分子の電子構造

Research Project

Project/Area Number	12740324
Research Institution	Osaka City University
Principal Investigator	佐藤和信大阪市立大学, 大学院・理学研究科, 講師 (90264796)
Keywords	ESR / パルスESR / 電子スピンニューテーション / 高スピン有機分子 / デカサイクレン / 多価アニオン状態 / ヤーンテラー効果 / 微細構造
Research Abstract	3回対称軸をもつ高対称性有機磁性体モデルとして、非局在化型カルベンや比較的安定なニトレンを3個導入した高スピン有機分子(I、II)や高対称有機分子デカサイクレンのトリアニオン高スピン状態(III)をcw-ESR法及びパルスESR/二次元電子スピンニューテーション法を用いて明らかにした。分子I、IIは、いずれも前駆体となるジアゾ化合物、アジド化合物を有機ガラス溶媒中に希釈した無秩序配向試料をアルゴンイオンレーザーを用いた光分解により反応中間体である高スピン分子を発生し、ESRの測定を行った。二次完スピンニューテーション分光法によるスペクトルの分離・スピン多重度の同定を行った後、スペクトルシミュレーション法を用いて微細構造定数を高精度で決定した。微細構造定数の理論的考察から、高スピン分子の電子状態・分子構造を明らかにした。特に、IIのニトレン系分子ではこれまで文献で報告されている値が誤っていることを証明し、電子状態と分子構造を統一的に理解できる微細構造定数を決定すると共に、報告されている値を修正した。IIIは、アルカリ金属と中性分子との化学還元を行うことにより生成し、ESRの測定を行った。トリアニオンに由来する四重項状態のESRスペクトルを観測し、基底四重項状態であることを明らかにした。ESR及び密度汎関数法を用いた分子軌道計算の結果と総合的に考察することにより、デカイサイクレンのトリアニオン状態において、分子構造のヤーンテラー歪みによるエネルギーの安定化が大きくないことを示した。これは、従来のトリアニオンが基底二重項状態であるとする説を覆すものである。また、四重項状態の微細構造定数の理論的考察から、IIIのような非局在化した高対称性の四重項状態の微細構造定数を取り扱うためには、3つの不対電子が相互作用する3体問題を顕わに考慮する必要があることを指摘した。

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

パルス電子スピン共鳴分光法による高対称高スピン有機分子の電子構造

Principal Investigator

佐藤 和信 大阪市立大学, 大学院・理学研究科, 講師 (90264796)

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).

佐藤和信大阪市立大学, 大学院・理学研究科, 講師 (90264796)