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安定有機ラジカルや遷移金属錯体を用いた分子性強磁性体の開発に関する研究

Research Project

Project/Area Number 09740464
Research Category

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

Allocation TypeSingle-year Grants
Research Field Organic chemistry
Research InstitutionThe University of Electro-Communications

Principal Investigator

石田 尚行 (石田 高行)  電気通信大学, 電気通信学部, 助教授 (00232306)

Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1998: ¥600,000 (Direct Cost: ¥600,000)
Keywordsラジカル / 強磁性体 / 弱強磁性体 / 錯体 / 有機強磁性体 / 磁性体 / Tc共役系 / 分子性強磁性体 / コバルトイオン
Research Abstract

当研究グループは、完全に有機元素のみからなるTEMPO系強磁性体を開発しており、本年度も継続してその磁性の発現機構の詳細について調べた。強磁性体物質の選択的重水素化を行い、固体の^1Hおよび^2DのNMR測定から、各水素原子上のスピン密度を割り出した。これは分子間の磁気的相互作用のチャンネルに対する知見を与える。また、圧力下でこの物質が反強磁性体に転じることを明らかにした。この奇妙な現象は、何らかの分子間接触の変化が、ある方向の相互作用の符号だけを反転させているものと考えられる。
新しい材料の開発として、π共役系を持つ有機ラジカル類に展開した。なかでもビス(ビフェニリル)ニトロキシドの誘導体では、パラ位置換基に長鎖アルキルを用いたものすべてに強磁性的相互作用が得られた。この一連の傾向と、アルキル置換基の「ファスナー効果」との関連は興味深い。また、TTFとπ共役したラジカルドナー分子や、パラフェニレンジアミン部分を共役して有するキレート遷移金属錯体の合成を行い、後者ではさらに種々のアクセプターとの電荷移動錯体を得た。
π共役系有機材料を架橋配位子とし三次元的ネットワークを有する遷移金属錯体の探索では、強弱磁性体、ピリミジン鉄(II)錯体を見いだした。ピリミジン銅(II)の反強磁性的一次元鎖においては、従来鎖末端に起因すると考えられてきたキューリー磁性の寄与が、実は鎖構造に本質的なものであったということを明らかにした。架橋共役アニオンとして、シアナミドアニオン、ジピリジルアミンアニオンを検討し、相転位温度が10Kないし20K級の磁性体を得た。

Report

(2 results)
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] K.Nakayamaら: "Pyrimidine-Bridged Cobalt(II)Complexes with a Chiral 3-D Network Showing Weak Ferromagnetism" Chemistry Letters. 497-498 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Luoら: "Electrical Conductivities and Crystal and Band-Electronic Structures of a New Phase of BEDT-TTF-Bromide Salt,(BEDT-TTF)2Br(H2O)3" Syuthetic Metals. 96. 97-102 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Ishidaら: "Ferromagnetic and Antiferromagnetic Phases of 4-(4-Iodobenzylideneamino)-2,2,6,6-tetramethylpiperidin-1-yloxyl" Bullctin of the Chemical Society of Japan. 71. 2583-2587 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] G.Marntaら: "Solid-State High-Resolution 1H and 2D NMR Study of the Electron Spin Distribution of the Hydrogen-Bonded Organic Ferromagnetic Compound 4-Hydroxyimino-TEMPO" Journal of the American Chemical Society. 121. 424-431 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Nakagawaら: "Intermolecular Ferromagnetic Interaction in the Crystal of a Diphenyl Nitroxide Derivative.The Role of Spin-Polarized Hydrogen Atoms Located near a Neighboring N-O Site" Chemical Physics Letters. (印刷中).

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Nogami: "TEMPO-Based Organic Ferromagnets and Metamagnets(TEMPO=2,2,6,6-Tetramethylpiperidin-1-yloxyl)" Molecular Crystals and Liquid Crystals. 296. 305-322 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] R.Imachi: "piSR of the Organic Radical Ferromagnet,4-(p-Chlorobenzylideneamino)-2,2,6,6-tetramethylpiperidin-1-yloxyl" Chemistry Letters. 233-234 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Ishida: "Pyrimidine-Bridged Transition Metal Complexes as a Polymer Approach to Molecule-Based Ferromagnets" Recent Reserch Development in Pure and Applied Chemistry. 1. 1-15 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] R.Imachi: "Ferromagnetic Dimer of pi-Conjugated Organic Free Radicals 9,9-Bis(p-tolyl)-9,10-dihydroacridin-10-yl-oxyl" Chemistry Letters. 743-744 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Nakayama: "Ferromagnetic Interaction in a Pyrimidine-Bridged Copper(II)Nitrate Complexes" Molecular Crystals and Liquid Crystals. 306. 379-384 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Nogami: "Ferromagnetism of Organic Radical Crystals of Perdeuterated TEMPO Derivatives" Molecular Crystals and Liquid Crystals. 305. 211-216 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Kawakami: "Magnetic Interaction via β-hydrogen atoms in TEMPO Derivatives" Molecular Crystals and Liquid Crystals. 306. 141-150 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] G.Murata: "Solid State ^1H-MAS-NMR and Spin Densities on Protons of the Organic Ferromagnetic TEMPO Derivatives" Molecular Crystals and Liquid Crystals. 306. 307-314 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] R.Imachi: "Ferromagnetism of Organic Radical Crystals of Deuterated TEMPO Derivatives" Synthetic Metals. 85. 1743-1744 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Ishida: "Magnetic Properties of Pyrimidine-Bridged Copper(II)Complexes" Synthetic Metals. 85. 1655-1658 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Yoshida: "Electrical Conductivities of MOTT Salts" Synthetic Metals. 86. 2135-2136 (1997)

    • Related Report
      1997 Annual Research Report

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

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