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Magnetic Properties of Iron(III) exhibiting Spin-Equilibrium Behavior and Imidazolate-bridged Binuclear Complexes.

Research Project

Project/Area Number 61470047
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionKumamoto University

Principal Investigator

AKIRA OHYOSHI  Professor, Department of Applied Chemistry, Faculty of Engineering. Kumamoto Univesity., 工学部, 教授 (00040379)

Co-Investigator(Kenkyū-buntansha) NAOHIDE MATSUMOTO  Assistant, Department of Applied Chemistry, Faculty of Engineering, Kumamoto Uni, 工学部, 助手 (80145284)
本坊 寿吉  熊本大学, 工学部, 助教授 (80040369)
Project Period (FY) 1986 – 1988
Project Status Completed (Fiscal Year 1988)
Budget Amount *help
¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 1988: ¥200,000 (Direct Cost: ¥200,000)
Fiscal Year 1987: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1986: ¥5,000,000 (Direct Cost: ¥5,000,000)
KeywordsSpin-equilibrium / Iron(III) complex / Magnetic susceptibility / Imidazolate-bridged complex / Binuclear complex / 磁化率 / イミダゾレート架橋銅二核錯体 / 反強磁性相互作用 / 銅(II)-マンガン(II)-銅(II)三核錯体 / 單結晶X線構造解析 / 多核銅(II)錯体 / ヘリコイド状直鎖構造 / イミダゾレート架橋二核金属錯体 / 酵素のモデル錯体 / 構造パラメーター / 相互作用定数 / イミダゾレート配位シツフ塩基鉄【III】錯体 / スピン平衡 / メスバウアースペクトル / スピン遷移速度 / 分子構造 / イミダゾレート架橋二核銅【II】錯体 / 反強磁性パラメーター
Research Abstract

1. Synthesis and Magnetic Properties of Iron(III) Complexes Exhibiting a Spin-Equilibrium Behavior.
(1). Five binuclear iron(III) complexes bridged by hyrazine, 1,1'-tetraethylenebis(imidazol), or bis-(pyridine) compounds have been prepared, and their spin-equilibrium behavior between high spin (s=5/2) and low-spin(s=1/2) states has been investigates by means of the temperature dependences of the magnetic susceptibilities and the electronic spectra. The pyridine complex is low-spin, while the bis(imidazole) and the bis(pyridine) complexes showed a spin-equilibrium between high-spin and low-spin states, accompanied by a striking thermochromism in both the solids and solutions.
(2). An Iron(III) complex [bis[3-(3-methoxysalicylideneamine)propyl]amino-O,N,N',N",O'](pyridine)-iron(III) Tetraphenylborate with a spinequilibrium has been investigated by means of the temperature dependences of the magnetic susceptibilities, the electronic spectra, and cyclic voltammetry. The pure electronic spec … More tra for high-spin and low-spin species were evaluated from the observed electronic spectra and the equilibrium constants obtained from the magnetic data. The electrontransfer entropy of the Fe<@D13+@>D1 + e Fe<@D2+@>D1 process (deltaS<@D2et@>D2) was obtained as 205 JK<@D1-1@>D1mol<@D1-1@>D1 from the temperature dependence of the cyclic voltammogram.
2. synthesis and magnetic properties of imidazolate-bridged binulear complexes.
(1). Imidazolate-bridged Cu(II)-Mn(II)- Cu(II) complexes have been prepared and characterized. The magnetic susceptibility data were represented by a spin-only interaction model(1/2-5/2-1/2) with J_<Mn-Cu> value of -13 cm^<-1> for (tfa) complex and -8 cm^<-1> for (hfa) complex.
(2). Two imidazolate-bridged binuclear copper(II) complexes[Cu(L)Cu(tfacac)_2]and [Cu(L)Cu(tebima)]-[PF_6][C10_4] ・Me_2CO have been prepared and characterized by elemental analyses, melting points, molar electrical conductivities, i.r., electronic, and e.s.r.spectra, magnetic susceptibilities. The magnetic susceptobolity data gave the antiferromagnetic interaction parameters 2J = 112 cm^<-1> for the former complex and ー140 cm^<-1> for the latter. The e.s.r.spectra of complexes measured in frozen solutions (77K) at X-band frequency showed broad deltaM=1 and weak deltaM=2 absorptions. Less

Report

(4 results)
  • 1988 Annual Research Report   Final Research Report Summary
  • 1987 Annual Research Report
  • 1986 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] N.Matsumoto;T.Akui;H.Murakami;A.Ohyoshi;H.Okawa;J.Kanesaka: Journal of the Chemical Society,Dalton Transaction. 1988. 1021-1035 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N.Matsumoto;T.Akui;A.Ohyoshi;H.Okawa: Bulletin of the chemical Society of JAPAN. 61. 2250-2252 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N.Matsumoto;S.Yamashita;A.Ohyoshi;S.Kohata;H.Okawa: Journal of the Chemical Society,Dalton Transactions. 1988. 1943-1948 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N.Matsumoto;N.Takemoto;A.Ohyoshi;H.Okawa: Bulletin of the Chemical Society of JAPAN. 61. 2987-2986 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] T.Akui;A.Ohyoshi;N.Matsumoto;H.Okawa: Bulletin of the Chemical Societ of JAPAN. 61. 4155-4157 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] K.Toriumi;T.Kanao;Y.Umetsu;A.Ohyoshi;M.Yamashita;T.Ito: Jouranal of Coordination Chemistry. 19. 209-221 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Shoichi,Ohta: "The Synthesis, Magnetic, and Spectroscopic Properties of Binuclear Iron(III) Complexes Bridged by Pyrazine, 1, 1'-Tetramethylenebis(imidazole0, or Bis(pyridine) Compounds Exhibiting a Spin-Equilibrium Behavior." Bulletin of the Chemical Society of Japan. 59. 155-159 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Naohide,Matsumoto: "Synthesis and Characterization of Imidazolate-Bridged Binuclear Copper(II) Complexes." Bulletin of the Chemical Society of Japan. 59. 1609-1610 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Akira,Ohyoshi: "Spin-Equilibrium Behavior in Solution of an Iron(III) Complex [Bis[3-(3-methoxysalicylidene)propy1]amino-O,N,N^1,N^<11>,O^1](pyridine)iron(III) Tetraphenylbolate." Bulletin of the Chemical Society of Japan. 59. 1611-1613 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yonezo,Maeda: "Spectroscopic and Magnetic Properties of [Fel_2(salacen)]PF_6(L=Imidazole or N-Methylimidazole); New Examples of Intermediate Electron Relaxation Between S=1/2 and 5/2 States. X-Ray Crystal Structure of [Fe(Him)_2(salacen]PF_6." Journal of the Chemical Society, Dalton Transactions. 1986. 1115-1123 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Naohide,Matsumoto: "Synthesis and Characterization of Imidazolate-Bridged Trinuclear (Copper(II)-Manganese(II)-Copper(II)) Complexes." Bulletin of the Chemical Society of Japan. 60. 3056-3058 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N.Matsumoto;T.Akui.;H.Murakami,;A.Ohyoshi,;H.Okawa,;J.Kanesaka: Journal of the Chemical Society,Dalton Transaction.1988. 1021-1035 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] N.Matsumoto,;T.Akui,;A.Ohyoshi,;H.Okawa.: Bulletin of the Chemical Society of JAPAN. 61. 2250-2252 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] N.Matsumoto,;S.Yamashita,;A.Ohyoshi,;S.Kohata,;H.Okawa.: Journal of the Chemical Society,Dalton Transactions. 1988. 1943-1948 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] N.Matsumoto,;N.Takemoto,;A.Ohyoshi,;H.Okawa.: Bulletin of the Chemical Society of JAPAN. 61. 2984-2986 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] T.Akui,;A.Ohyoshi,;N.Matsumoto,;H.Okawa.: Bulletin of the Chemical Societ of JAPAN. 61. 4155-4157 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Toriumi,;T.Kanao,;Y.Umetsu,;A.Ohyoshi,;M.Yamashita,;T.Ito.: Jouranal of Coordination Chemistry. 19. 209-221 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] Akira Ohyoshi;Jukichi Honbo;Naohide Matsumoto;Shoichi Ohta;Singo Sakamoto: Bulletin of the Chemical Society of JAPAN. 59. 1611-1613 (1986)

    • Related Report
      1987 Annual Research Report
  • [Publications] Yonezo Maeda;Yoshimasa Takashima;Naohide Matsumoto;Akira Ohyoshi: Journal of the Chemical Society,Dalton Transactions. 1986. 1115-1123 (1986)

    • Related Report
      1987 Annual Research Report
  • [Publications] Kazushi Mashima;Kouki Jyodoi;Akira Ohyoshi;Hidemasa Takaya: Journal of the Chemical Society,Chemical Communications. 1986. 1145-1146 (1986)

    • Related Report
      1987 Annual Research Report
  • [Publications] Kazushi Mashima;Kouki Jyodoi;Akira Ohyoshi;Hidemasa Takaya: Organometallics(American Chemical Society). 1987. 885-887 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] Naohide Matsumoto;Junko KaneSaka;Akira Ohyoshi;Masaaki Nakamura;Susumu Kohata;Hisashi Okawa: Bulletin of the Chemical Society of JAPAN. 60. 3056-3058 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] Y.Maeda: J.Chem.Soc.Dalton Trans.1986. 1115-1123 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] N.Matsumoto: Bull.Chem.Soc.Jpn.59. 1609-1610 (1986)

    • Related Report
      1986 Annual Research Report

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Published: 1987-03-31   Modified: 2016-04-21  

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