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Development of Electrical Conductors with Magnetisms Based on Metal Complexes with Sulfur-rich Dithiolate Ligands as an Extended π-Electron System

Research Project

Project/Area Number 15550049
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionOsaka University

Principal Investigator

MATSUBAYASHI Gen-etsu  Osaka University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (90029182)

Project Period (FY) 2003 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2004: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2003: ¥2,500,000 (Direct Cost: ¥2,500,000)
KeywordsDithiolate complex / Rhodium complex / Iridium complex / Gold complex / Platinum complex / Manganese complex / Electrical conductivity / Magnetic susceptibility / クロム錯体 / シクロペンタジエニル錯体 / X線結晶解析
Research Abstract

Various metal complexes with sulfur-rich dithiolate ligands as an extended π-electron system have been synthesized, and by the oxidation of them new electrical conductors have been obtained and for some of them the magnetic properties have been also clarified.
○ Cyclopentadienyl-rhodium(III) and -iridium(III) complexes with the C_3S_5 or C_8H_4S_8 ligand as well as the related pentamethylcyclopentadienyl-metal complexes have been synthesized, and the oxidized species of them have been obtained by reactions with bromine or iodine. The oxidation process which leads to the dithiolate ligand-centered oxidation has been clarified. Structures and properties of the oxidized species have been studied by X-ray crystal structure analysis and ESR spectra, and their electrical conductivities have been measured.
○ [Mn(C_8H_4S_8)_2]^<2-> complexes containing the Mn(II) ion have been synthesized. The magnetic susceptibilities have clarified the spin state of S = 5/2 and a tetrahedral geometry around th … More e Mn(II) ion in the solid state. The reaction of the [Mn(C_8H_4S_8)_2]^<2-> complex with iodine has afforded [Mn(C_8H_4S_8)_2]^0 having the Mn(III) state and the one-electron oxidized C_8H_4S_8 ligands, which results in the spin state of S = 3/2. This oxidized species exhibits strong anti-ferromagnetic interaction among the complex moieties (Θ= -60 K) with the electrical conductivity of 3.0 x 10^<-2> S cm^<-1> measured for a compacted pellet at room temperature.
○ Polar metal complexes [M(ppy)(L)]^<n-> (M = Pd(II), Pt(II) and Au(III); L= C_3S_5^<2-> or C_8H_4S_8^<2->; ppy =_C-deprotonated 2-phenylpyridine; n = 1, 2) have been synthesized. The oxidized species obtained by reactions of them with iodine or TCNQ show high electrical conductivities. Crystals of [Au(ppy)(C_8H_4S_8)]_2[PF_6] obtained by the oxidation through electrolysis of [Au(ppy)(C_8H_4S_8)] exhibit metallic behavior near room temperature. They have an electrical conduction pathway formed by two-dimensional interaction through S--S contacts among the planar, oxidized C_8H_4S_8 moieties. Less

Report

(3 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • Research Products

    (24 results)

All 2005 2004 2003 Other

All Journal Article (20 results) Publications (4 results)

  • [Journal Article] Oxidation of [Ir(η^5-C_5Me_5)(C_8H_4S_8)] and Crystal Stuctures of [IrI-(η^5-C_5Me_5)(C_8H_4S_8)](I_3) and [IrI-(η^5-C_5Me_5)(C_8H_4S_8)](I_3)_<1/2>(I_7)_<1/2>2005

    • Author(s)
      K.Kawabata, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Inorg.Chim.Acta 358

      Pages: 2082-2088

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Oxidation of [Ir(η^5-C_5Me_5)-(C_5Me_5)] and Crystal Structures of [IrI(η^5-C_5Me_5)-(C_8H_4S_8)](I_3) and [IrI(η^5-C_5Me_5)(C_8H_4S_8)](I_3)_<1/2>(I_7)_<1/2>2005

    • Author(s)
      K.Kawabata, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Inorg.Chim.Acta 358

      Pages: 2082-2088

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Structures and Electrical Conductivities of Cation Radical Salts Based on Unsymmetrical [Au(III)(C-N)(S-S)] Type Dithiolate Complexes2005

    • Author(s)
      K.Kubo, A.Nakano, Y.Ishii, R.Kato, G.Matsubayashi
    • Journal Title

      Synthetic Metals 印刷中

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Crystal Structures of [Rh(η^5-C_5H_5)(C_3S_5)] and [Rh(η^5-C_5Me_5)(C_3S_5)] and Properties of Their Oxidized Species2004

    • Author(s)
      K.Kawabata, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      J.Organomet.Chem. 689

      Pages: 405-410

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Properties of Organometal-Sulfur-rich Dithiolate Complexes [M(L)(C_8H_4S_8)] (M = Rh^<III> and Ir^<III>;L = η^5-C_5H_5 and η^5-C_5Me_5) and Their Oxidation2004

    • Author(s)
      K.Kawabata, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Eur.J.Inorg.Chem.

      Pages: 2137-2143

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Structures of Sulfur-rich Dithiolate-Gold(I) Complexes and Their Oxidation2004

    • Author(s)
      T.Ryowa, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Inorg.Chim.Acta 357

      Pages: 3532-3540

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Oxidation of [Ir(η^5-C_5Me_5)(C_3S_5)][C_3S_5^<2-> = 4,5-Disulfanyl-1,3-dithiole-2-thionate(2-)] and X-Ray Crystal Stucture of [IrBr(η^5-C_5Me_5)(μ^5-C_2S_4)-IrBr(η^5-C_5Me_5)]2004

    • Author(s)
      K.Kawabata, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Inorg.Chim.Acta 357

      Pages: 4373-4378

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Preparation and Oxidation of Pt(II) Complexes Containing both C-Deprotonated 2-phenylpyridine (ppy^-) and a Sulfur-rich Dithiolate Ligand and X-ray Crystal Structure of [NBu^n_4][Pt(ppy)(C_8H_4S_8)]2004

    • Author(s)
      Y.Suga, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Bull.Chem.Soc.Jpn. 77

      Pages: 1877-1883

    • NAID

      10013737676

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Crystal Structures of [Rh-(η^5-C_5H_5)(C_3S_5)] and [Rh(η^5-C_5Me_5)(C_3S_5)]and Properties of Their Oxidized Species2004

    • Author(s)
      K.Kawabata, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      J.Organomet.Chem. 689-No.2

      Pages: 405-410

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Properties of Organometal-Sulfur-rich Dithiolate Complexes [M(L)-(C_8H_4S_8)] (M = Rn^<III> and Ir^<III> ; L = η^5-C_5H_5 and (η^5-C_5Me_5) and Their Oxidation2004

    • Author(s)
      K.Kawabata, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Eur.J.Inorg.Chem.

      Pages: 2137-2143

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Structures of Sulfur-rich Dithiolate-Gold(I) Complexes and Their Oxidation2004

    • Author(s)
      T.Ryowa, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Inorg.Chim.Acta 357-No.5

      Pages: 3532-3540

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Oxidation of [Ir(η^5-C_5Me_5)(C_3S_5)] [C_3S_5^<2->-=4,5-Disulfanyl-1,3-dithiole-2-thionate(2-)]2004

    • Author(s)
      K.Kawabata, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Inorg.Chim.Acta 357-No.8

      Pages: 4373-4378

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Preparation and Oxidation of Pt(II)Complexes Containing both C-Deprotonated 2-phenylpyridine (ppy-) and a Sulfur-rich Dithiolate Ligand and X-ray Crystal Structure of [NBu^n_4][Pt-(PPY)(C_8H_4S_8)]2004

    • Author(s)
      Y.Suga, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Bull.Chem.Soc.Soc. 77-No.10

      Pages: 1877-1883

    • NAID

      10013737676

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Properties of Organometal-Sulfur-rich Dithiolate Complexes [M(L)(C_8H_4S_8)] (M=Rh^<III> and Ir^<III>;L=η^5-C_5H_5 and η^5-C_5Me_5) and Their Oxidation2004

    • Author(s)
      K.Kawabata, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Eur.J.Inorg.Chem. 4

      Pages: 2137-2143

    • Related Report
      2004 Annual Research Report
  • [Journal Article] ESR Study of Spin-crossover Complex [Mn^<III>(taa)] Using Pulsed High Magnetic Field2004

    • Author(s)
      S.Kimura, T.Otani, Y, Narumi, K.Kindo, M.Nakano, G.Matsubayashi
    • Journal Title

      J.Magn.Mater. 272-276

      Pages: 1102-1103

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Structures of Sulfur-rich Dithiolate-Gold(I) Complexes and Their Oxidation2004

    • Author(s)
      T.Ryowa, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Inorg.Chim.Acta 357,5

      Pages: 3532-3540

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Oxidation of [Ir(η^5-C_5Me_5)(C_3S_5)] [C_3S_5^<2->=4,5-Disulfanyl-1,3-dithiole-2-thio-nate(2-)] and X-Ray Crystal Structure of [IrBr(η^5-C_5Me_5)(μ-C_2S_4)IrBr(η^5-C_5Me_5)]2004

    • Author(s)
      K.Kawabata, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Inorg.Chim.Acta 357,8

      Pages: 4373-4378

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Preparation and Oxidation of Pt(II) Complexes Containing both C-Deprotonated 2-phenylpyridine (ppy^-) and a Sulfur-rich Dithiolate Ligand and X-ray Crystal Structure of [NBu^<n->_4][Pt(ppy)(C_8H_4S_8)]2004

    • Author(s)
      Y.Suga, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Bull.Chem.Soc.Jpn. 77,10

      Pages: 1877-1883

    • Related Report
      2004 Annual Research Report
  • [Journal Article] X-ray Crystal Structure and Electrical Conductivity of [Au(ppy)(C_8H_4S_8)]_<2^->[PF_6] [ppy^- = C-Deprotonated-2-phenylpyridine(-);C_8H_4S_8^<2-> = 2-{(4,5-Ethylenedithio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithionate(2-)]2003

    • Author(s)
      K.Kubo, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Eur.J.Inorg.Chem. 22

      Pages: 4093-4098

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] X-ray Crystal Structure and Electrical Conductivity of [Au(ppy)(C_8H_4S_8)]_2-[PF_6] [ppy^- = C-Deprotonated-2-phenyl-pyridine(-); C_8H_4S_8^<2-> = 2-{(4,5-Ethylenedi-thio)-1,3-dithiole-pyridine(-); 2-ylideile}-1,3-dithiole-4,5-dithionate(2-)]2003

    • Author(s)
      K.Kubo, M.Nakano, H.Tamura, G.Matsubayashi
    • Journal Title

      Eur.J.Inorg.Chem. 22-No.2

      Pages: 4093-4098

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] K.Kubo, M.Nakano, H.Tamura, G.Matsubayashi: "X-ray Crystal Structure and Electrical Conductivity of [Au(ppy)(C_8H_4S_8)]_2[PF_6][ppy-=C-Deprotonated-2-phenylpyridine(-) ; C_8H_4S_8^<2->=2-{(4,5-Ethylenedithio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithionate(2-)]"European Journal of Inorganic Chemistry. 22・12. 4093-4098 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Kawabata, M.Nakano, H.Tamura, G.Matsubayashi: "Crystal Structures of [Rh(η^5-C_5H_5)(C_3S_5)] and [Rh(η^5-C_5Me_5)(C_3S_5)] and Properties of their Oxidized Species"Journal of Organometallic Chemistry. 689・2. 405-410 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Kawabata, M.Nakano, H.Tamura, G.Matsubayashi: "Properties of Organometal-Sulfur-rich Dithiolate Complexes [M(L)(C_8H_4S_8)](M=Rh^<III> and Ir^<III> ; L=η^5-C_5H_5 and η^5-C_5Me_5) and Their Oxidation"European Journal of Inorganic Chemistry. (印刷中). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] 松林玄悦, 黒沢英夫, 芳賀正明, 松下隆之: "錯体・有機金属の化学"丸善株式会社. 204 (2004)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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