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Preparation and properties of conducting complexes based on 3-D conjugation system by δ-π interaction

Research Project

Project/Area Number 14350453
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 工業物理化学
Research InstitutionGifu University

Principal Investigator

KAWAMURA Takashi  Gifu University, Faculty of Engineering, Professor, 工学部, 教授 (40026125)

Co-Investigator(Kenkyū-buntansha) EBIHARA Masahiro  Gifu University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (80201961)
Project Period (FY) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥14,400,000 (Direct Cost: ¥14,400,000)
Fiscal Year 2003: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2002: ¥10,800,000 (Direct Cost: ¥10,800,000)
Keywordsrhodium / dinuclear complexes / mixed oxidation state / electrical conductivities / ruthenium / tetrathiafulvalene / electron configuration / δ-π interaction / コバルト / δπ相互作用 / 結晶構造 / 伝導性
Research Abstract

This project explored novel transition metal cluster complexes with moderate to high electrical conductivities based on δ-π interaction in paddlewheel-type dinuclear complexes. (1)We prepared dirhodium complexes with tetrathiafulalenyldiphenylphosphine as axial ligands and also those with tetrathiafulvalenylcarboxylate bridging ligands. In their crystals, intermolecular π-stack of TTF moieties has been observed. Their electrochemical behaviors showed that intermolecular TTF-TTF electronic interaction is not very strong. (2)Crystal structures of diruthenium complexes with 2-aminothiazolate bridging ligand showed that the RuRu δ^* orbital is located above the RuRu πorbital in energy due to δ-π interaction and the stronp donating nature of the bridging ligand. (3) A mixed oxidation-state complex having a diamondoid extended structure has been prepared from dirhodium tetraacetamidate, its cation radical and ssodium iodide. It is a semiconductor and its electrical conductivity oscillates over a order of 10^5 upon dehydration-rehydration cycles of its hydration water molecules. (4) The crystal of the cationic radical salt of a dirhodium complex with 4-phenanthridinolate bridging ligand has been shown to, a semiconductor. (5) A series of Co-Rh mixed mixed-element trinuclear complexes has been studied. The metal-metal interaction in this series of complexes has been shown to have a trend that heavier metal has stronger M-M interaction.

Report

(3 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • Research Products

    (6 results)

All Other

All Publications (6 results)

  • [Publications] M.Ebihara, N.Nagaya, N.Kawashima, T.Kawamura: "Diruthenium complexes with aminothiazolato ligand. X-ray and electronic structures of [Ru_2(dmat)_4Cl]^<0/+> (dmat=4,5-dimethyl-2-methylaminothiazolato)"Inorg.Chim.Acta. 351. 305-310 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Ebihara, M.Iiba, S.Higashi, N.Tsuzuki, T.Kawamura, T.Morioka, S.Ozawa, T.Yamabe, H.Masuda: "Benzylidine-capped group 9 trinuclear clusters ; synthesis, structure and properties of trirhodium and cobalt-rhodium mixed metal clusters [Co_<3-n>Rh_nCp_3(μ_3-CPh)_2] (n=1,2,3)"Polyhedron. 22. 3413-3422 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Ebihara, N.Nagaya, N.Kawashima, T.Kawamura: "Diruthenium complexes with antinothiazolato ligand. X-ray and electronic structures of [Ru_2(dmat)_4Cl]^<0/+> (dmat =4,5-dimethyl-2-methylaminothiazolato)"Inorg.Chim.Acta. vol.351. 305-310 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Ebihara, M.Iiba, S.Higashi, N.Tsuzuki, T.Kawamura, T.Morioka, S.Ozawa, T.Yamabe, H.Masuda: "Benzylidine-capped group 9 trinuclear clusters ; synthesis, structure and properties of trirhodium and cobalt-rhodium mixed metal clusters [Co_<3-n>Rh_nCp_3(μ_3-CPh)_2] (n=1,2,3)"Polyhedron. vol.22. 3413-3422 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Ebihara, M.Iiba, S.Higashi, N.Tsuzuki, T.Kawamura, T.Morioka, S.Ozawa, T.Yamabe, H.Masuda: "Benzylidine-capped group 9 trinuclear clusters ; synthesis, structure and properties of trirhodium and cobalt-rhodium mixed metal clusters [Co_<3-n>Rh_nCp_3(μ_3-CPh)_2](n=1,2,3)"Polyhedron. 22. 3413-3422 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Ebihara, N.Nagaya, N.Kawashima, T.Kawamura: "Diruthenium complexes with aminothiazolato ligand. X-ray and electronic structures of [Ru_2(dmat)_4Cl]^<0/+> (dmat = 4,5-dimethyl-2-methylaminothiazolato)"Inorg. Chim. Acta. (印刷中). (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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