2000 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, 理学部, 講師 (90264796)
Keywords	ESR / 電子スピンニューテーション / 高スピン有機分子 / 非局在型分子 / ジアントリルカルベン / シクロペンタンジイルビラジラル / ESRスペクトルシミュレーション / 微細構造定数
Research Abstract	高い対称性の二次元型超高スピン有機分子モデルとして、3つの9,9′-ジアントリルカルベンを1,3,5-トリエチニルベンゼンにカップルさせたトリカルベン分子(1)やシクロペンタンジイルビラジラルをベンゼン環の1,3,5位でカップルさせたヘキサラジカル(2)などの非局在化型高スピン有機分子、及び1,3,5-トリス(p-ニトレノフェニル)ベンゼン(3)の電子・分子構造を、無秩序配向cw ESR法及び電子スピンニューテーション法を用いて解明した。それぞれのジアゾ、アジド前駆体を反磁性物質中に希釈した無秩序配向試料を用いて、ヘリウム温度領域で超高圧水銀灯やアルゴンイオンレーザーにより光照射を行うことにより高スピン分子を生成し、ESRの測定を行った。分子1〜3は、いずれも複数の異なる電子スピン多重度をもつ高スピン種が混在する複雑なスペクトルを示した。磁場掃引を行いながらニューテーションスペクトルを測定する多次元化法により、複雑なESRスペクトルから七重項・五重項・三重項分子種を分離・同定し、スペクトルシミュレーション法を用いてそれぞれの高スピン種の微細構造定数を決定した。微細構造定数から分子構造を明らかにすることを目的として、スピンユニットの三重項微細構造テンソルを用いた半経験的な解析を行った。分子1,2の微細構造定数には、π電子が極度に非局在化した電子構造であるために、スピンユニットの微細構造テンソルだけでなく、スピンユニット間のスピン-スピン双極子相互作用(二中心相互作用)が無視できない程度に影響していることを明らかにし、極度に非局在化したπ電子系を介して電子スピンが強磁性的に相互作用することにより形成された高スピン分子の電子構造・分子構造を決定した。多次元化電子スピンニューテーション法を高スピン複雑系モデルに適用することにより、複雑な超高スピン分子系の物件評価手法としての優位性を実証した。

Research Products
(46 results)

All Other

All Publications (46 results)

[Publications] Kazunobu Sato et al.: "Spin Characterization of Lanthanoid Ion Eu^<2+> (^8S_<7/2>) in a CaF_2 Single Crystal by Two-Dimensional Electron Spin Transient Nutation Spectroscopy"Two-Dimensional Correlation Spectroscopy, 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-butyl-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] 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] 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] Nobuyuki 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.: "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] 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] 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 hydrogen-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-butyl-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"Magnetix 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] Tukahisa Nishio et al.: "^<14>N-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.: "CW/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] Kazunobu 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 Tanake 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"Molecular Crystals and Liquid Crystals. (印刷中). (2001)

2000 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, 理学部, 講師 (90264796)

Research Products

[Publications] Kazunobu Sato et al.: "Spin Characterization of Lanthanoid Ion Eu^<2+> (^8S_<7/2>) in a CaF_2 Single Crystal by Two-Dimensional Electron Spin Transient Nutation Spectroscopy"Two-Dimensional Correlation Spectroscopy, 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-butyl-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] 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] 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] Nobuyuki 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.: "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] 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] 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 hydrogen-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-butyl-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"Magnetix 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] Tukahisa Nishio et al.: "^<14>N-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.: "CW/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] Kazunobu 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 Tanake 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"Molecular Crystals and Liquid Crystals. (印刷中). (2001)

佐藤和信大阪市立大学, 理学部, 講師 (90264796)