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Development of Electrical Conductors with Multi-dimensionality Based on Non-planar Metal Complexes with Sulfur-rich Ligands as an Extended pi-System

Research Project

Project/Area Number 09640665
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionOasaka 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) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 1998: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1997: ¥2,300,000 (Direct Cost: ¥2,300,000)
KeywordsDithiolate complex / Molybdenum complex / Platinum complex / Cobalt complex / Titanium complex / Ruthenium complex / Oxidation / Electrical conductivity / シクロペンタジエニル錯体 / スズ錯体 / 酸化還元電位
Research Abstract

Various metal complexes with dithiolato ligands containing many sulfur atoms asan extended it-system have been synthesized, and by the oxidation of them new electrical conductors have been obtained and their properties c1arified.
[NEt_4]_2[Mo(O)(etdt)_2](etdt=C_8H_4S_4^<2->) having five-coordinate square-pyramid geometry has been prepared. The oxidized species [NEt_4]_<0.3>[Mo(O)(etdt)_2] and [Fe(C_5Me_5)_2]_<0.05>[Mo(O)(etdt)_2] exhibited high electrical conduc-tivities (0.29 and 5.9 S cm^<-1>, respectively, at room temperature for compacted pellets). In the oxidized species S-S interactions among the etdt-ligand moieties form effective electron-conduction pathways.
Co(III)- and Ti(IV)- complexes having cyclopentadienyl groups and dmit (C_3S_5^<2->) or etdt ligand have been investigated.
Oxidation behavior of reactions of Co (L) (dmit) (L = eta^5-C_5H_5, eta^5-C_5Me_5) with bromine and the crystal structure of the one-electron oxidized species Co(eta^5-C_5Me_5)(dmit)Br have been clarifie … More d, together with a strong antiferromagnetic interaction between the oxidized dmit-ligand moieties.
Co(eta^5-C_5H_5)(etdt) and Ti(eta^5-C_5H_5)_2(etdt) have been synthesized and properties of their oxidized complexes studied. Especially, [Co(eta^5-C_5H_5)(etdt)] I_3 and [Co(eta^5-C_5H_5)(etdt)][PF_6]_<0.7> exhibited high electrical conductivities of 0.19 and 0.16 S cm^<-1>,
respectively, at room temperature measured for compacted pellets.
Electrical conductivities of oxidized species of dmit- and etdt-Ru(II) cpmplexes have been studied. Ru(bpy)_2(dmit) and Ru(bpy)_2(etdt) (bpy = 2,2'-bipyridine) having a bulky six-coordinate geometry have been synthesized. The oxidized species obtained by reactions with iodine, Ru(bpy)_2(etdt)] I and Ru(bpy)_2(etdt)] (I_3)_<2.1>, have electrical conductivities of 7.4 x 10^<-7> and 7.0 x 10^<-4> S cm^<-1>, respectively. Even in the highly bulky complexes coordinated with two bpy ligands, extended oxidation on the etdt-ligand moiety leads to effective molecular interaction through S-S contacts among etdt-Iigand moieties. Less

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] 中野元裕: "Preparation and properties of C_8H_4S_8-platinum(II)complexes and electrical conductivities of their oxidized species and X-ray crystal structure of C_8H_4S_8(CH_2CH_2CN)_2 as a pro-ligand compound" Inorganica Chimica Acta. 279・1. 165-171 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 森 博之: "Paramagnetic Organocobalt(III)Dithiolate Complex : Crystal Structure and Magnetic Property of Co(η^5-C_5Me_5)(C_3S_5)Br," Chemistry Letters. No.8. 729-730 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 中濱亜理: "Properties of Pt(II)-complexes Containing Both a Pyridyl N-N Chelate Ligand Having a Long Alkyl Chain and a Sulfur-rich Dithiolate Ligand and their Molecular Interactions in the Solid State" Inorganica Chimica Acta. 284・1. 55-60 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 森 博之: "Oxidation Properties of Co(η^5-C_5H_5)(C_8H_4S_8)and CoL(C_3S_5)(L=η^5-C_5H_5 and η^5-C_5Me_5)and C_8H_4S_8^<2->)and crystal structur of Co(η^5-C_5H_5)(C_3S_5)Br," Journal of Organometallic Chemistry. 574・1. 77-85 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Nakano, A.Kuroda, H.Tamura, R.Arakawa, and G.Matsubayashi: "Preparation and Properties of C_8H_4S_8-platinum (II) Complexes and Electrical Con-ductivities of Their Oxidized Species and X-ray Crystal Structure of C_8H_4S_8(CH_2CH_2CN)_2 as a Pro-ligand Compound." Inorg.Chim.Acta. 279-No.2. 165-171 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Mori, M.Nakano, H.Tamura, G.Matsubayashi, and W.Mori: "Paramagnetic Organocobalt (III) Dithiolate Complex : Crystal Structure and Magnetic Property ofCo (eta^5-C_5Me_5) (C_3S_5) Br." Chem.Lett.No.8. 729-730 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Nakahama, M.Nakano, and G.Matsubayashi: "Properties of Pt (III) -complexes Containing Both a Pyridyl N-N Chelate Ligand Having a Long Alkyl Chain and a Sulfur-rich Dithiolate Ligand and their Molecular Interactions in the Solid State." Inorg.Chim.Acta. 284-No.1. 55-60 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Mori, M.Nakano, H.Tamura, and G.Matsubayashi: "Oxidation Properties of Co (eta^5-C_5H_5) - (C_8H_4S_8) and CoL (C_3S_5) (L=eta^5-C_5H_5and eta^5-C_5Me_5) and Crystal Structure of Co(eta^5-C_5H_5) (C_3S_5) Br." J.Organomet.Chem.574-No.1. 77-85 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 森 博之: "Paramagnetic Organocobalt(III) Dithiolate Complex: Crystal Structure and Magnetic Property of Co(η^5-C_5Me_5)(C_3S_5)Br," Chemistry Letters. No.8. 729-730 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 中濱亜理: "Properties of Pt(II)-complexes Containing Both a Pyridyl N-N Chelate Ligand Having a Long Alkyl Chain and a Sulfur-rich Dithiolate Ligand and their Molecular Interactions in the Solid State" Inorganica Chimica Acta. 284・ 1. 55-60 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] 森 博之: "Oxidation Properties of Co(η^5-C_5H_5)(C_8H_4S_8) and CoL(C_3S_5)(L=η^5-C_5H_5 and η^5-C_5Me_5) and C_8H_4S_8^<2->) and crystal structure of Co(η^5-C_5H_5)(C_3S_5)Br," Journal of Organometallic Chemistry. 574・1. 77-85 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] 中野元裕: "Preparation and properities of C_8H_4S_8-platinum (II) complexes and electrical conductivities of their oxidized species and X-ray crystal structure of C_8H_4S_8 (CH_2CH_2CN) _2 as a pro-ligand compound" Inorganica Chimica Acta. (印刷中).

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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