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電子スピンユーテーション法による電荷を有する高スピン有機分子の電子構造

Research Project

Project/Area Number 10740275
Research Category

Grant-in-Aid for Encouragement of Young Scientists (A)

Allocation TypeSingle-year Grants
Research Field Physical chemistry
Research InstitutionOsaka City University

Principal Investigator

佐藤 和信  大阪市立大学, 理学部, 講師 (90264796)

Project Period (FY) 1998 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1999: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1998: ¥1,500,000 (Direct Cost: ¥1,500,000)
Keywords高スピン有機分子 / 多価アニオン / トリニトレン / ESR / 電子スピンニューテーション / 遷移モーメント分光 / パルスESR / ニューテーション / 高スピンクラスター
Research Abstract

安定な超高スピン有機分子の開発と新規な量子効果の出現を目的とする基礎的研究として、高い対称性を有する高スピン有機分子を分子設計・合成し、ESR法・二次元電子スピンニューテーション(2D-ESTN)法を用いて電子状態・分子構造を調べた。LUMO近傍に3つのの擬縮重分子軌道を有するデカサイクレンは、金属接触を用いた多段階還元により生成する3価のアニオン状態においてLUMOに導入される電子スピンが電子対を作らず、基底状態において4重項状態を形成することを示した。そして、ESRスペクトルから決定した微細構造定数をもとに4重項状態における電子構造を明らかにすると共に、電荷の揺らぎとスピン分極の相関を検討した。一方、テルフェニル或いは1,3,5-トリフェニルベンゼンなどのポリフェニルを骨格に複数のニトレン前駆体を導入した分子を合成し、超高圧水銀ランプを用いた光照射により生成する高スピン分子の電子・分子構造を微細構造ESRスペクトルの測定から明らかにした。特に、1,3,5-トリフェニルベンゼンを骨格にもつトリニトレン高スピン分子が基底7重項状態であることをESRスペクトルの温度依存性から証明し、スペクトルシミュレーション法により決定したトリニトレンの微細構造定数からその分子構造の対称性が低下していることを示した。また、2D-ESTN法が異なるスピンの混在系や複雑な超微細構造を示す系に適用し、複雑なESRスペクトルの分離・同定に有用であることを示した。ESTN分光におけるニューテーション周波数が遷移モーメントと密接に関係していることを理論と実験の両面から明らかにし、ニューテーション分光法を準位間のエネルギー差により遷移を区別する従来の分光法と異なる新しい遷移モーメント分光法として確立した。

Report

(2 results)
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] Kazunobu Sato et al.: "Persistent high spin polycarbene (S=3) as studied by 2D-ESTN spectroscopy"Synthetic Metals. 103. 2269-2270 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Kazunobu Sato et al.: "2D-electron spin transient nutation (2D-ESTN) study of a persistent high-spin carbene (S=3)"Mol. Cryst. Liq. Cryst.. 334. 81-88 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Kazunobu Sato et al.: "Spin characterization of lanthanoid ion Eu^<2+>(^8S_<7/2>) in a CaF_2 single crystal by electron spin transient nutation spectroscopy"Mol. Cryst. Liq. Cryst.. 335. 333-342 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Shigeaki Nakazawa et al.: "Electronic states and spin characterization of polyanionic high-spin molecules and clusters derived from 1,3-debenzoylbenzene derivatives"Mol. Cryst. Liq. Cryst.. 334. 11-22 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takeo Nakai et al.: "ESR study of high spin nitrenes width s-triazine skeleton"Synthetic Metals. 103. 2265-2266 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takeo Nakai et al.: "High-spin nitrenes with s-triazine skeleton"Mol. Cryst. Liq. Cryst.. 335. 157-166 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takeo Nakai et al.: "Exchange interaction of some thianthrene-derived dications"Mol. Cryst. Liq. Cryst.. 334. 139-148 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Kozo Fukui et al.: "Spin density distribution of 2,5,8-tri-tert-butylphenalenyl radical by ESR/ENDOR and NMR studies"Synthetic Metals. 103. 2257-2258 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Kozo Fukui et al.: "Electronic structure of a stable phenalenyl radical as studied by ESR/ENDOR and NMR spectroscopy"Mol. Cryst. Liq. Cryst.. 334. 49-58 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Jae Young Bae et al.: "Random Orientation ESR Studies of Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation"Bull.Magn. Reson.. 19. 39-43 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Jae Young Bae et al.: "Spin alignment in high spin carbenes of heteroatomic piconjugation"Synthetic Metals. 103. 2261-2262 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Jae Young Bae et al.: "Spin Alignment in High-Spin Carbenes of Heteroatomic π-Conjugation"Mol. Cryst. Liq. Cryst.. 334. 59-168 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.C.B.L. Shohoji et al.: "Polyanionic high spin hydrocarbons width high symmetry"Synthetic Metals. 102. 1544-1545 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.C.B.L. Shohoji et al.: "Electronic Quartet and Triplet States of Polyanionic C_<60> Fullerrene and Their Anomalous Spin Relaxation"J. Am. Chem. Soc.. (印刷中). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Hideo Tomioka: "Persistent High-Spin Polycarbene.Generation of Polybromonated 1,3,5-Tris-[2-[4-(Phenylcarbeno)=phenyl]ethynyl]benzene(S=3)and Spin Identification by Two-Dimensional Electron Spin Transient Nutation Spectroscopy" J.Am.Chem.Soc.120. 1106-1107 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takeo Nakai: "Tribenzo-1,4,5,8,9,12-hexathiatriphenylene Dication and Dibenzo-1,4,5,8-tetrathiaphenanthrene Dication" Chem.Lett.933-934 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Kazunobu Sato: "Persistent high spin polycarbene(S=3)as studied by 2D-ESTN spectroscopy" Synthetic Metals. (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Shigeaki Nakazawa: "Polyanionic high spin hydeocarbons width high symmetry" Synthetic Metals. (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Kazunobu Sato: "2D-electron spin transient nutation(2D-ESTN)study of a persistent high-spin carbene(S=3)" Molecular Crystals and Liquid Crystals. (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Kazunobu Sato: "Spin characterization of lanthanoid ion Eu^<2+>(^8S_<7/2>)in a CaF_2 single crystal by electron spin transient nutation spectroscopy" Molecular Crystals and Liquid Crystals. (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Kazunobu Sato: "electron spin transient nutation phenomena of Lanthanide ion Eu^<2+>(^8S_<7/2>)in a CaF_2 single crystal by pulsed ESR spectroscopy" Magnetic Resonance & Related Phenomena. (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Shigeaki Nakazawa: "ESR and Electron Spin Transient Nutation Study of Polyanionic High-Spin Clusters of 1,3-Dibenzoyl Benzene Derivatives" Magnetic Resonance & Related Phenomena. (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takeo Nakai: "Single-Crystal ESR of High Spin Nitrene with s-Triazine Skelton" Magnetic Resonance & Related Phenomena. (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Luisa,T.M.B.Franco: "A novel intramolecular quarted ground state of decacyclene trianion" Molecular Crystals and Liquid Crystals. (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Shigeaki Nakazawa: "Electronic states and spin characterization of polyanionic high-spin molecules and clusters derived from 1,3-dibenzoylbenzene derivatives as studied by ESR/electron spin transient nutation spectroscopy" Molecular Crystals and Liquid Crystals. (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takeji Takui: "Spinics;prospects for spin-mediated molecular electronics" Molecular Crystals and Liquid Crystals. (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Tekeji Takui: "Magnetic Properties of Organic Materials" Marcel Dekker Inc.Publisher, 450 (1999)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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