2000 Fiscal Year Annual Research Report

有機高スピン分子スピニクスの化学-直接的スピン同定分光の開発

Research Project

Project/Area Number	12020248
Research Institution	Osaka City University
Principal Investigator	佐藤和信大阪市立大学, 理学部, 講師 (90264796)
Keywords	パルスESR / 電子スピンニューテーション / フラーレン多価アニオン / スピン格子緩和 / フォノンボトルネック現象 / 共鳴スピントンネル現象 / ヤーンテラー歪み / 遷移モーメント分光
Research Abstract	有機超伝導や有機強磁性を直接発現した新規な分子性物質として発見されて以来大きな注目を集めてきたフラーレンの多価アニオンの電子構造と分子構造を解明し、その量子的性質の発現機構の解明する手がかりを得ることを目的として、電子スピンニューテーション法とパルスESR法を適用した。カリウム金属ミラーを用いた接触還元法によって、フラーレンジアニオン及びドリアニオンを生成した。スピン状態はそれぞれ三重項、四重項状態になることをcw-ESRおよび二次元電子スピンニューテーション法の測定により同定し、微細構造定数を決定し、分子構造における対称性の低下を明らかにした。また、ESRスペクトルの温度依存性から、サンプルを室温から4.2Kに急冷したときのみ、それぞれ三重項、四重項状態が基底状態となり、10K付近で低スピン状態との逆転が起こり、それぞれ基底一重項、二重項に変化する特異な電子状態をフラーレシ多価アニオン状態がもつことを発見した。パルスESRを用いた緩和時間の測定において、10K以上で観測される熱励起の三重項、四重項状態においてフォノンボトルネック現象が生じ、さらにスピン格子緩和曲線にうねりが生じるスピン格子緩和の異常を初めて観測した。これらの現象をScott-Jeffriesの式、および核の振動を考慮した二重振動子非対称ポテンシャルを用いたシュレデンガー方程式に基づいて考察を行い、ボトルネック現象によってスピン格子緩和速度が遅くなったことと励起スピン状態が近接しているため、すなわちポテンシャル壁の高さが低いためにインコヒーレント共鳴スピントンネル現象がスピン格子緩和曲線のうねりとして観測されたものであると結論した。この共鳴スピントンネル現象は、アルカリ金属をドープしたフラーレン結晶系のhigh-Tc超伝導発現機構を説明する低スピン状態における動的なヤーン・テラー理論を支持する最初の実験的証拠である。

Research Products

(46 results)

All Other

All Publications (46 results)

[Publications] Kazunobu Sato et al.: "Spin Characterization of Lanthanoid Ion Eu^<2+> (^8S7/2) in a CaF_2 Single Crystal by Two-Dimensional Electron Spin Transient Nutation Spectroscopy"Two-Dimensional Correlation Speclroscopy, American Institute of Physics. 337-340 (2000)
[Publications] Takeji Takui et al.: "Two-Dimensional FT-Pulsed Electron Spin Transient Nutation Spectroscopy"Two-Dimensional Correlation Spectroscopy, American Institute of Physics. 134-143 (2000)
[Publications] M.Candida B.L.Shohoji et al.: "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"Two-Dimensional Correlation Spectroscopy, American Institute of Physics. 333-336 (2000)
[Publications] Yasushi Morita et al.: "New Persistent Radicals : Synthesis and Electronic Spin Structure of 2,5-Di-tert-buty1-6-Oxophenalenoxyl Derivatives"Journal of American Chemical Society. 122. 4825-4826 (2000)
[Publications] Koji Kamiyama et al.: "Benzoic Acid and Phenol Derivatives of Nitronyl Nitroxide Biradical as Building Blocks of Organic Molecule-Based Ferrimagnetcs"Applied Magnetic Resonance. 19. 45-57 (2000)
[Publications] Masahiro Nishizawa et al.: "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"Journal of Physical Chemistry. 104. 503-509 (2000)
[Publications] Daisuke Shiomi et al.: "Spin-Spin Correlation Function and Magnetic Susceptibility of Quantum Ferrimagnetic Spin Chains as Models for Organic Molecule-Based Ferrimagnetics"Journal of Physical Chemistry. 104. 1961-1965 (2000)
[Publications] M.Candida B.L.Shohoji et al.: "Electronic Quartet and Triplet States of Polyanionic C_<60> Fullerrene and Their Anomalous Spin Relaxation As Studied by cw-ESR/2D-Electron Spin Nutation Spectroscopy"Journal of American Chemical Society. 122. 2962-2963 (2000)
[Publications] Akira Izuoka et al.: "Spin Alignment in Singly Oxidized Spin-Polarized Diradical Donor : Thianthrene Bis(nitronyl nitroxide)"Journal of American Chemical Society. 122. 3234-3235 (2000)
[Publications] Shuichiro Hase et al.: "Phenol-substituted nitronyl nitroxide biradicals with a triplet (S=1) ground state"Journal of Materials Chemistry. 11. 756-760 (2001)
[Publications] Kazunobu Sato et al.: "Pulsed ESR/2D-electron spin transient nutation study of stable high-spin polycarbenes"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Kozo Fukui et al.: "ESR/^1H-ENDOR (TRIPLE) studies on generation and decay processes of a triangulene derivative, the first non-kekule polynuclear aromatic hydrocarbon"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Hideto Matsuoka et al.: "Transition moment spectroscopy-based simulation of two-dimensional electron spin transient nutation spectra of Eu^<2+>ion in a CaF_2 single crystal"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Shigeaki Nakazawa et al.: "Spin quartet and triplet states of polyanionic C_<60> fullerenes and their anomalous spin relaxation as studied by CW-ESR/2D-electron spin transient nutation spectroscopy"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Shigeaki Nakazawa et al.: "Polyanionic C_<60>-based high-spin molecular clusters as studied by pulsed ESR/2D electron spin transient nutation spectroscopy"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Koya Tanaka et al.: "Electronic and molecular structures of di[dianthrylcarbene] coupled by 1,4-diethynylbenzene as studied by cw/pulsed ESR spectroscopy"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Nobuyuld Oda et al.: "Molecular and electronic structures of high-spin polyphenylene-based oligo nitrenes as studied by ESR spectroscopy"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Kozo Fukui et al.: "Electron-nuclear magnetic resonance studies on electronic spin structure of novel persistent neutral radical with 1,3-diaza-phenalene skeleton"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Kozo Fukui et al.: "Electronic spin identification of paramagnetic centers in crystalline solids of C_<60> and its derivatives as studied by ESR/2D electron spin transient nutation spectroscopy"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Motoko Sakai et al.: "Low-dimensional molecule-based magnets ; structures and magnetic properties of copper (II) complexes with hydrogene-bonded network"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Ko Furukawa et al.: "Dynamic magnetic properties from microstructured ferromagnetic thin films with 1-d periodic lattice structure"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Yasushi Morita et al.: "New persistent radicals : Synthesis and electronic spin structure of 2,5-di-t-buty1-6-oxophenalonoxyl derivatives"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Daisuke Shiomi et al.: "Quantum ferrimagnetic spin chains as studied by numerical calculations of a heisenberg spin hamiltonian and ESR experiments"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Shuichiro Hase et al.: "Magnetic properties of phenol-substituted nitronyl nitroxide biradicals and their anion radical salts"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Takayasu Kanaya et al.: "Nitroxide triradicals as building blocks of molecule-based ferrimagnetics"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Koji Kamiyama et al.: "Intramolecular magnetic interactions and solid state magnetic properties of phenol and benzoic acid derivatives of nitronyl nitroxide biradicals"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Thkahisa Nishio et al.: "^4N-ENDOR and spin lattice relaxation study of high-spin ferric iron (II) octaethylporphyrin"Magnetic Resonance and Related Phenomena. (印刷中). (2001)
[Publications] Hideto Matsuoka et al.: "Transition Moment Spectroscopy Based on Pulsed EPR : Complete Assignment of Complicated EPR Spectra from Electronic and Nuclear High-Spin Systems"Polyhedron. (印刷中). (2001)
[Publications] Takayasu Kanaya et al.: "Single-Component Ferrimagnetics : Triplet-Doublet Composite Molecules as Constituents of Purely Organic Molecule-Based Ferrimagnets"Polyhedron. (印刷中). (2001)
[Publications] Motoko Sakai et al.: "Structures and Magnetic Properties of Cu (II) Complexes with Hydrogen-Bonded Network ; Novel Functionality of Low-Dimensional Molecule-Based Magnets"Polyhedron. (印刷中). (2001)
[Publications] Shuichiro Hase et al.: "Magnetic Properties of Phenol-Substituted Nitronyl Nitroxide Biradicals as Building Blocks of Organic Salt Ferrimagnets"Polyhedron. (印刷中). (2001)
[Publications] Kazunobu Sato et al.: "Pulsed ESR/2D-electron spin transient nutation study of stable high spin polycarbenes"Synthetic Metals. (印刷中). (2001)
[Publications] Koya Tanaka et al.: "GW/pulsed ESR study of Bis[dianthrylcarbene] coupled by 1,4-Diethylbenzene"Synthetic Metals. (印刷中). (2001)
[Publications] Shigeaki Nakazawa et al.: "Electronic states of polyanionic high-spin C_<60> fullerene and their clusters : Anomalous spin relaxation and Jahn-Teller effects"Synthetic Metals. (印刷中). (2001)
[Publications] Kozo Fukui et al.: "Electronic spin structure of novel persistent neutral radical with 1,3-Diaza-phenalene skeleton as studied by electron-nuclear magnetic resonance"Synthetic Metals. (印刷中). (2001)
[Publications] Motoko Sakai et al.: "Low-dimentional molecule-based magnets with hydrogen-bonded network"Synthetic Metals. (印刷中). (2001)
[Publications] Kozo Fukui et al.: "X-and W-band ESR study on γ-cyclodextrin bicapped C_<60> after NH_3-gas doping"Synthetic Metals. (印刷中). (2001)
[Publications] Tukahisa Nishio et al.: "Ground-state high-spin ferric iron (III) octaethylporphyrin as studied by single-crystal pulsed ESR/CW ^<14>N-ENDOR spectrscopy"Synthetic Metals. (印刷中). (2001)
[Publications] Daisuke Shiomi et al.: "Molecular design of organic ferrimagnets"Synthetic Metals. (印刷中). (2001)
[Publications] Nobuyuki Oda et al.: "Highly symmetric high-spin oligonitrenes ; Molecular design for super high-spin systems with robust π-spin polarization"Synthetic Metals. (印刷中). (2001)
[Publications] Kozo 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"Synthetic Metals. (印刷中). (2001)
[Publications] Kazunobtu 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"Molecular Crystals and Liquid Crystals. (印刷中). (2001)
[Publications] Daisuke Shiomi et al.: "Organic molecule-based ferrimagnetism : Magnetic properties of a model compound and numerical calculations of a model spin Hamiltonian"Molecular Crystals and Liquid Crystals. (印刷中). (2001)
[Publications] Suguru Maki et al.: "Hydrogen-bonded open-shell molecules : Synthesis and physical properties of the oxophenalenoxyl-based radical with hydroxyl group"Molecular Crystals and Liquid Crystals. (印刷中). (2001)
[Publications] Nobuyuki Oda et al.: "Molecular and electronic spin structures of high-spin polyphenylene-based oligonitrenes with high symmetry : A semiempirical approach to fine-structure tensors"Molecular Crystals and Liquid Crystals. (印刷中). (2001)
[Publications] Koya 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"Molectular Crystals and Liquid Crystals. (印刷中). (2001)

2000 Fiscal Year Annual Research Report

有機高スピン分子スピニクスの化学-直接的スピン同定分光の開発

Principal Investigator

佐藤 和信 大阪市立大学, 理学部, 講師 (90264796)

Research Products

[Publications] Kazunobu Sato et al.: "Spin Characterization of Lanthanoid Ion Eu^<2+> (^8S7/2) in a CaF_2 Single Crystal by Two-Dimensional Electron Spin Transient Nutation Spectroscopy"Two-Dimensional Correlation Speclroscopy, American Institute of Physics. 337-340 (2000)

[Publications] Takeji Takui et al.: "Two-Dimensional FT-Pulsed Electron Spin Transient Nutation Spectroscopy"Two-Dimensional Correlation Spectroscopy, American Institute of Physics. 134-143 (2000)

[Publications] Yasushi Morita et al.: "New Persistent Radicals : Synthesis and Electronic Spin Structure of 2,5-Di-tert-buty1-6-Oxophenalenoxyl Derivatives"Journal of American Chemical Society. 122. 4825-4826 (2000)

[Publications] Koji Kamiyama et al.: "Benzoic Acid and Phenol Derivatives of Nitronyl Nitroxide Biradical as Building Blocks of Organic Molecule-Based Ferrimagnetcs"Applied Magnetic Resonance. 19. 45-57 (2000)

[Publications] Masahiro Nishizawa et al.: "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"Journal of Physical Chemistry. 104. 503-509 (2000)

[Publications] Daisuke Shiomi et al.: "Spin-Spin Correlation Function and Magnetic Susceptibility of Quantum Ferrimagnetic Spin Chains as Models for Organic Molecule-Based Ferrimagnetics"Journal of Physical Chemistry. 104. 1961-1965 (2000)

[Publications] M.Candida B.L.Shohoji et al.: "Electronic Quartet and Triplet States of Polyanionic C_<60> Fullerrene and Their Anomalous Spin Relaxation As Studied by cw-ESR/2D-Electron Spin Nutation Spectroscopy"Journal of American Chemical Society. 122. 2962-2963 (2000)

[Publications] Akira Izuoka et al.: "Spin Alignment in Singly Oxidized Spin-Polarized Diradical Donor : Thianthrene Bis(nitronyl nitroxide)"Journal of American Chemical Society. 122. 3234-3235 (2000)

[Publications] Shuichiro Hase et al.: "Phenol-substituted nitronyl nitroxide biradicals with a triplet (S=1) ground state"Journal of Materials Chemistry. 11. 756-760 (2001)

[Publications] Kazunobu Sato et al.: "Pulsed ESR/2D-electron spin transient nutation study of stable high-spin polycarbenes"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Kozo Fukui et al.: "ESR/^1H-ENDOR (TRIPLE) studies on generation and decay processes of a triangulene derivative, the first non-kekule polynuclear aromatic hydrocarbon"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Hideto Matsuoka et al.: "Transition moment spectroscopy-based simulation of two-dimensional electron spin transient nutation spectra of Eu^<2+>ion in a CaF_2 single crystal"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Shigeaki Nakazawa et al.: "Spin quartet and triplet states of polyanionic C_<60> fullerenes and their anomalous spin relaxation as studied by CW-ESR/2D-electron spin transient nutation spectroscopy"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Shigeaki Nakazawa et al.: "Polyanionic C_<60>-based high-spin molecular clusters as studied by pulsed ESR/2D electron spin transient nutation spectroscopy"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Koya Tanaka et al.: "Electronic and molecular structures of di[dianthrylcarbene] coupled by 1,4-diethynylbenzene as studied by cw/pulsed ESR spectroscopy"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Nobuyuld Oda et al.: "Molecular and electronic structures of high-spin polyphenylene-based oligo nitrenes as studied by ESR spectroscopy"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Kozo Fukui et al.: "Electron-nuclear magnetic resonance studies on electronic spin structure of novel persistent neutral radical with 1,3-diaza-phenalene skeleton"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Kozo Fukui et al.: "Electronic spin identification of paramagnetic centers in crystalline solids of C_<60> and its derivatives as studied by ESR/2D electron spin transient nutation spectroscopy"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Motoko Sakai et al.: "Low-dimensional molecule-based magnets ; structures and magnetic properties of copper (II) complexes with hydrogene-bonded network"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Ko Furukawa et al.: "Dynamic magnetic properties from microstructured ferromagnetic thin films with 1-d periodic lattice structure"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Yasushi Morita et al.: "New persistent radicals : Synthesis and electronic spin structure of 2,5-di-t-buty1-6-oxophenalonoxyl derivatives"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Daisuke Shiomi et al.: "Quantum ferrimagnetic spin chains as studied by numerical calculations of a heisenberg spin hamiltonian and ESR experiments"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Shuichiro Hase et al.: "Magnetic properties of phenol-substituted nitronyl nitroxide biradicals and their anion radical salts"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Takayasu Kanaya et al.: "Nitroxide triradicals as building blocks of molecule-based ferrimagnetics"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Koji Kamiyama et al.: "Intramolecular magnetic interactions and solid state magnetic properties of phenol and benzoic acid derivatives of nitronyl nitroxide biradicals"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Thkahisa Nishio et al.: "^4N-ENDOR and spin lattice relaxation study of high-spin ferric iron (II) octaethylporphyrin"Magnetic Resonance and Related Phenomena. (印刷中). (2001)

[Publications] Hideto Matsuoka et al.: "Transition Moment Spectroscopy Based on Pulsed EPR : Complete Assignment of Complicated EPR Spectra from Electronic and Nuclear High-Spin Systems"Polyhedron. (印刷中). (2001)

[Publications] Takayasu Kanaya et al.: "Single-Component Ferrimagnetics : Triplet-Doublet Composite Molecules as Constituents of Purely Organic Molecule-Based Ferrimagnets"Polyhedron. (印刷中). (2001)

[Publications] Motoko Sakai et al.: "Structures and Magnetic Properties of Cu (II) Complexes with Hydrogen-Bonded Network ; Novel Functionality of Low-Dimensional Molecule-Based Magnets"Polyhedron. (印刷中). (2001)

[Publications] Shuichiro Hase et al.: "Magnetic Properties of Phenol-Substituted Nitronyl Nitroxide Biradicals as Building Blocks of Organic Salt Ferrimagnets"Polyhedron. (印刷中). (2001)

[Publications] Kazunobu Sato et al.: "Pulsed ESR/2D-electron spin transient nutation study of stable high spin polycarbenes"Synthetic Metals. (印刷中). (2001)

[Publications] Koya Tanaka et al.: "GW/pulsed ESR study of Bis[dianthrylcarbene] coupled by 1,4-Diethylbenzene"Synthetic Metals. (印刷中). (2001)

[Publications] Shigeaki Nakazawa et al.: "Electronic states of polyanionic high-spin C_<60> fullerene and their clusters : Anomalous spin relaxation and Jahn-Teller effects"Synthetic Metals. (印刷中). (2001)

[Publications] Kozo Fukui et al.: "Electronic spin structure of novel persistent neutral radical with 1,3-Diaza-phenalene skeleton as studied by electron-nuclear magnetic resonance"Synthetic Metals. (印刷中). (2001)

[Publications] Motoko Sakai et al.: "Low-dimentional molecule-based magnets with hydrogen-bonded network"Synthetic Metals. (印刷中). (2001)

[Publications] Kozo Fukui et al.: "X-and W-band ESR study on γ-cyclodextrin bicapped C_<60> after NH_3-gas doping"Synthetic Metals. (印刷中). (2001)

[Publications] Tukahisa Nishio et al.: "Ground-state high-spin ferric iron (III) octaethylporphyrin as studied by single-crystal pulsed ESR/CW ^<14>N-ENDOR spectrscopy"Synthetic Metals. (印刷中). (2001)

[Publications] Daisuke Shiomi et al.: "Molecular design of organic ferrimagnets"Synthetic Metals. (印刷中). (2001)

[Publications] Nobuyuki Oda et al.: "Highly symmetric high-spin oligonitrenes ; Molecular design for super high-spin systems with robust π-spin polarization"Synthetic Metals. (印刷中). (2001)

[Publications] Kozo 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"Synthetic Metals. (印刷中). (2001)

[Publications] Kazunobtu 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"Molecular Crystals and Liquid Crystals. (印刷中). (2001)

[Publications] Daisuke Shiomi et al.: "Organic molecule-based ferrimagnetism : Magnetic properties of a model compound and numerical calculations of a model spin Hamiltonian"Molecular Crystals and Liquid Crystals. (印刷中). (2001)

[Publications] Suguru Maki et al.: "Hydrogen-bonded open-shell molecules : Synthesis and physical properties of the oxophenalenoxyl-based radical with hydroxyl group"Molecular Crystals and Liquid Crystals. (印刷中). (2001)

[Publications] Nobuyuki Oda et al.: "Molecular and electronic spin structures of high-spin polyphenylene-based oligonitrenes with high symmetry : A semiempirical approach to fine-structure tensors"Molecular Crystals and Liquid Crystals. (印刷中). (2001)

[Publications] Koya 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"Molectular Crystals and Liquid Crystals. (印刷中). (2001)

佐藤和信大阪市立大学, 理学部, 講師 (90264796)