1999 年度実績報告書

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

研究課題

研究課題/領域番号	11133252
研究機関	大阪市立大学
研究代表者	工位武治大阪市立大学, 理学部, 教授 (10117955)
キーワード	有機高スピン分子 / 非局在電子系 / 分子スピニクス / 有機磁性 / ニューテーション分光学 / 遷移モーメント分光学 / ESR / パルスESR
研究概要	(A)へテロ環共役系高スピン分子の合成と微細構造ESRスぺクトルの完全解析法の確立/普及開殻系π共役電子ネットワークにへテロ核原子を導入する場合、多価荷電高スピン分子では、へテロ核サイトの荷電化によってスピン状態は極端な変調をうけ、高スピン状態と低スピン状態の反転さえ予想できる。引き続き6員環に窒素核を導入した5重項メタフェニレンプロトタイプ(1)、ビフェニルプロトタイプ(2)、1,3,5―べンゼンプロトタイプ(3)のへテロ共役高スピン分子の前駆体であるポリアジド化合物(4)大きな非局在能をもつπトポロジー系を合成した。プロトタイプ(1)と(3)については、窒素核サイトの直接カチオン化による基底スピン状態の変化を解明する。今年度は複雑な微細構造スぺクトルの完全解析法(固有共鳴磁場)の確立と普及をはかった。 (B)任意高スピン系および複雑・スピン混合系のスピン状態の直接同定を可能にする新磁気共鳴分光法/Xバンド2次元電子スピンニューテーション法(2D-ESTN)の開発と確立/新しい適用A02班で新たに合成されることが予想される特異な非局在開殻電子系のスピン構造の同定に寄与するためのものであり、引き続き以下に示す(1)、(2)の他10ケースのケテゴリーの下に、直接スピン同定を目的とした2D-ESTNの開発を行った;(1)群論的に高い対称性をもつ分子構造やクラスター構造をもち、強いスピン間相互作用が高対称場にある高スピン系、(2)低対称場だがスピン量子数Sが著しく大きな擬超高スピン系。平成11年度は、最終的にはS=12をもつπ系の直接同定を試み、分子スピン多重度の記録を更新するために目下実験を継続中である。一方、C_<60>フラーレン多価アニオン系について、初めて3価アニオン系の基底4重項状態を検出しただけでなく、高スピン状態と低スピン状態間の転換過程を見いだし、その過程の物理的な起源を解明した。その結果、これまでの多くの論争と矛盾した解釈に決着をつけた。

研究成果
(29件)

すべてその他

すべて文献書誌 (29件)

[文献書誌] Jae Yaung Bae: "Random Orientation ESR Studies of Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation"Bulletin of Magenetic Resonance. 19. 39-43 (1999)
[文献書誌] K. Gotoh: "A Stable Neutral Hydrocarbon Radical: Synthesis, Crystal Structure and Physical Properties of 2, 5, 8-Tri-tert-butyl-phenalenly"J. Am. Chem. Soc. 121. 1619-1620 (1999)
[文献書誌] Shigeaki Nakazawa: "Electronic States and Spin Characterirzation of Polyanionic High-Spin Melecules and Clusters Derived from 1, 3-Dibenzoylbenzene Derivatires as Studied by ESR/Electron' Spin Transient Nutation Spectroscop"Mol. Cryst. and Liq. Cryst.. 334. 11-21 (1999)
[文献書誌] Kozo Fukui: "Electronic Structure of a Stable Phenalenyl Radical ad Studied by ESR/ENDOR, Paramagnetic NMR Spectroscopy and SQUID Measurements"Mol. Cryst. and Liq. Cryst.. 334. 49-58 (1999)
[文献書誌] Jae Young Bae: "Spin Alignment in High-Spin Carbenes of Heteroatomic π-Coujugation ; Invalidity of Simple Extension of "π-Topology Rule" for Homoatomic Systems"Mol. Cryst. and Liq. Cryst.. 334. 59-68 (1999)
[文献書誌] Kazunobu Sato: "2D-Election Spin Transient Nutation (2D-ESTN) Study of Stable High-Spin Carbene (S=3)"Mol .Cryst. and Liq. Cryst.. 334. 81-88 (1999)
[文献書誌] Daisuke Shiomi: "Charged Nitronye Nitroxide Biradicals as Building Blocks for Molecular Ferrimagnetics"Mol. Cryst. and Liq. Cryst.. 334. 99-108 (1999)
[文献書誌] Daisuke Shiomi: "Possible Superhigh-Spin Cluster in the Crystals of a Novle Nitronyl Nitroxide Radical as Studied by FT Pulsed ESR"Mol. Cryst. and Liq. Cryst.. 335. 359-369 (1999)
[文献書誌] Ko Furukawa: "A Novel Spin Wave from Low-Dimensional Superlattice of Microstructured Ferromagnetic Thin Films"Mol. Cryst. and Liq. Cryst.. 335. 163-172 (1999)
[文献書誌] K. Fukui: "Electronic Structure of a Stable Phenalenyl Radical in Crystalline State as Stuklied by SQUID Measurements, . CW-ESR, and ^<13>C CP/MAS MHR Spectroscopy"Synthetic Metals. 103. 2257-2258 (1999)
[文献書誌] M. C. B. L. Shohoji: "Polyanionic High-Spin Hydrocarbons with High Symmetry"Synthetic Metals. 102. 1544-1545 (1999)
[文献書誌] K. Sato: "Persistent High-Spin Polycarbene (S=3) as Studied by 2D-ESTN Spectroscopy"Synthetic Metals. 103. 2269-2270 (1999)
[文献書誌] J. Y. Bae: "Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation"Synthetic Metals. 103. 2261-2262 (1999)
[文献書誌] T. Nakai: "ESR Study of High-Spin Nitrenes with s-Triazine Skeleton"Synthetic Metals. 103. 2265-2266 (1999)
[文献書誌] K. Okada: "Structure and Photolysis of the Dimer of 2, 2-(m-Phenylene) bis-(4, 5-Diphenylmidazole-2-yl)Diradical"Synthetic Metals. 103. 2308-2309 (1999)
[文献書誌] D. Shiomi: "Magnetic Coupling of Nitronyl Nitroxide-Based Biradical Salts"Synthetic Metals. 103. 2271-2272 (1999)
[文献書誌] Masahiro Nishizawa: "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"J. Phys. Chem. B. 104. 503-509 (2000)
[文献書誌] Daisuke Shiomi: "Spin-Spin Correlation Function and Magnetic Susceptibility of Quantum Ferrimagnetic Spin Chains as Models for Organic Molecule-Based Ferrimagnetics"J. Phys. Chem. B. 104. 1961-1965 (2000)
[文献書誌] M. Candida B. L. Shohoji: "Electronic and Molecular Structures of Polyanionic C_<60> Fullerene and High-Spin C_<60>^<M-> Clusters Studied by ESR/2D-Election Spin Transient Nutation Spectroscopy"J. Am. Institute of Phys.. (in press). (2000)
[文献書誌] Kazunobu Sato: "A Stable High-Spin Polycarbene (S=3) as Studied by 2D-Electron Spin Transient Nutation Spectroscopy"J. Am. Institute of Phys.. (in press). (2000)
[文献書誌] Takeji Takui: "Two-Dimensional FT-Pulsed Electron Spin Transient Nutation Spectroscopy"J. Am. Institute of Phys.. (in press). (2000)
[文献書誌] K. Kamiyama: "Benzoic Acid and Phenol Derivatives of Nitronyl Nitroxide Biradical as Bulding Blocks of Organic Molecule-Based Ferrimagnetics"Applied Magnetic Resonance. (in press). (2000)
[文献書誌] M. Candida B. L. Shohoji: "Electronic Quartet and Triplet States of Polyanionic C_<60>Fullerrene and Their Anomalous Spin Relaxation as Studied by cw-ESR/2D-Electron Spin Transient Nutation Spectroscopy"J, Am. Chem. Soc.. 122(in press). (2000)
[文献書誌] Yasushi Morita: "New Persistent Radicals: Synthesis and Electronic Spin Structure of 2, 5,-Di-t-Butyl-6-Oxophenalenoxyl Derivatives"J, Am. Chem. Soc.. (in press). (2000)
[文献書誌] Akira Izuoka: "Spin Alignment in Singly Oxidized Spin-Polarized Diradical Donor: Thianthrene bis (nitronyl) nitroxide)"J, Am. Chem. Soc.. (in press). (2000)
[文献書誌] J. Y. Bae: "Randomly Orientation ESR Studies of Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation ; Eigenfield Analysis for High Spins and Off -Principal-Axis Extra Lines"Applied Magnetic Resonance. (in press). (2000)
[文献書誌] 工位武治: "化学の世界記録"化学同人. 580 (1999)
[文献書誌] Takeji Takui: "Magnetic Properties of Organic Materials"Mercel Dekker, Inc.. 590 (1999)
[文献書誌] Takeji Takui: "Molecular Magnetism"Kodansya Publisher (in press). (2000)

1999 年度 実績報告書

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

研究代表者

工位 武治 大阪市立大学, 理学部, 教授 (10117955)

研究成果

[文献書誌] Jae Yaung Bae: "Random Orientation ESR Studies of Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation"Bulletin of Magenetic Resonance. 19. 39-43 (1999)

[文献書誌] K. Gotoh: "A Stable Neutral Hydrocarbon Radical: Synthesis, Crystal Structure and Physical Properties of 2, 5, 8-Tri-tert-butyl-phenalenly"J. Am. Chem. Soc. 121. 1619-1620 (1999)

[文献書誌] Shigeaki Nakazawa: "Electronic States and Spin Characterirzation of Polyanionic High-Spin Melecules and Clusters Derived from 1, 3-Dibenzoylbenzene Derivatires as Studied by ESR/Electron' Spin Transient Nutation Spectroscop"Mol. Cryst. and Liq. Cryst.. 334. 11-21 (1999)

[文献書誌] Kozo Fukui: "Electronic Structure of a Stable Phenalenyl Radical ad Studied by ESR/ENDOR, Paramagnetic NMR Spectroscopy and SQUID Measurements"Mol. Cryst. and Liq. Cryst.. 334. 49-58 (1999)

[文献書誌] Jae Young Bae: "Spin Alignment in High-Spin Carbenes of Heteroatomic π-Coujugation ; Invalidity of Simple Extension of "π-Topology Rule" for Homoatomic Systems"Mol. Cryst. and Liq. Cryst.. 334. 59-68 (1999)

[文献書誌] Kazunobu Sato: "2D-Election Spin Transient Nutation (2D-ESTN) Study of Stable High-Spin Carbene (S=3)"Mol .Cryst. and Liq. Cryst.. 334. 81-88 (1999)

[文献書誌] Daisuke Shiomi: "Charged Nitronye Nitroxide Biradicals as Building Blocks for Molecular Ferrimagnetics"Mol. Cryst. and Liq. Cryst.. 334. 99-108 (1999)

[文献書誌] Daisuke Shiomi: "Possible Superhigh-Spin Cluster in the Crystals of a Novle Nitronyl Nitroxide Radical as Studied by FT Pulsed ESR"Mol. Cryst. and Liq. Cryst.. 335. 359-369 (1999)

[文献書誌] Ko Furukawa: "A Novel Spin Wave from Low-Dimensional Superlattice of Microstructured Ferromagnetic Thin Films"Mol. Cryst. and Liq. Cryst.. 335. 163-172 (1999)

[文献書誌] K. Fukui: "Electronic Structure of a Stable Phenalenyl Radical in Crystalline State as Stuklied by SQUID Measurements, . CW-ESR, and ^<13>C CP/MAS MHR Spectroscopy"Synthetic Metals. 103. 2257-2258 (1999)

[文献書誌] M. C. B. L. Shohoji: "Polyanionic High-Spin Hydrocarbons with High Symmetry"Synthetic Metals. 102. 1544-1545 (1999)

[文献書誌] K. Sato: "Persistent High-Spin Polycarbene (S=3) as Studied by 2D-ESTN Spectroscopy"Synthetic Metals. 103. 2269-2270 (1999)

[文献書誌] J. Y. Bae: "Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation"Synthetic Metals. 103. 2261-2262 (1999)

[文献書誌] T. Nakai: "ESR Study of High-Spin Nitrenes with s-Triazine Skeleton"Synthetic Metals. 103. 2265-2266 (1999)

[文献書誌] K. Okada: "Structure and Photolysis of the Dimer of 2, 2-(m-Phenylene) bis-(4, 5-Diphenylmidazole-2-yl)Diradical"Synthetic Metals. 103. 2308-2309 (1999)

[文献書誌] D. Shiomi: "Magnetic Coupling of Nitronyl Nitroxide-Based Biradical Salts"Synthetic Metals. 103. 2271-2272 (1999)

[文献書誌] Masahiro Nishizawa: "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"J. Phys. Chem. B. 104. 503-509 (2000)

[文献書誌] Daisuke Shiomi: "Spin-Spin Correlation Function and Magnetic Susceptibility of Quantum Ferrimagnetic Spin Chains as Models for Organic Molecule-Based Ferrimagnetics"J. Phys. Chem. B. 104. 1961-1965 (2000)

[文献書誌] M. Candida B. L. Shohoji: "Electronic and Molecular Structures of Polyanionic C_<60> Fullerene and High-Spin C_<60>^<M-> Clusters Studied by ESR/2D-Election Spin Transient Nutation Spectroscopy"J. Am. Institute of Phys.. (in press). (2000)

[文献書誌] Kazunobu Sato: "A Stable High-Spin Polycarbene (S=3) as Studied by 2D-Electron Spin Transient Nutation Spectroscopy"J. Am. Institute of Phys.. (in press). (2000)

[文献書誌] Takeji Takui: "Two-Dimensional FT-Pulsed Electron Spin Transient Nutation Spectroscopy"J. Am. Institute of Phys.. (in press). (2000)

[文献書誌] K. Kamiyama: "Benzoic Acid and Phenol Derivatives of Nitronyl Nitroxide Biradical as Bulding Blocks of Organic Molecule-Based Ferrimagnetics"Applied Magnetic Resonance. (in press). (2000)

[文献書誌] M. Candida B. L. Shohoji: "Electronic Quartet and Triplet States of Polyanionic C_<60>Fullerrene and Their Anomalous Spin Relaxation as Studied by cw-ESR/2D-Electron Spin Transient Nutation Spectroscopy"J, Am. Chem. Soc.. 122(in press). (2000)

[文献書誌] Yasushi Morita: "New Persistent Radicals: Synthesis and Electronic Spin Structure of 2, 5,-Di-t-Butyl-6-Oxophenalenoxyl Derivatives"J, Am. Chem. Soc.. (in press). (2000)

[文献書誌] Akira Izuoka: "Spin Alignment in Singly Oxidized Spin-Polarized Diradical Donor: Thianthrene bis (nitronyl) nitroxide)"J, Am. Chem. Soc.. (in press). (2000)

[文献書誌] J. Y. Bae: "Randomly Orientation ESR Studies of Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation ; Eigenfield Analysis for High Spins and Off -Principal-Axis Extra Lines"Applied Magnetic Resonance. (in press). (2000)

[文献書誌] 工位武治: "化学の世界記録"化学同人. 580 (1999)

[文献書誌] Takeji Takui: "Magnetic Properties of Organic Materials"Mercel Dekker, Inc.. 590 (1999)

[文献書誌] Takeji Takui: "Molecular Magnetism"Kodansya Publisher (in press). (2000)

1999 年度実績報告書

工位武治大阪市立大学, 理学部, 教授 (10117955)