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Mixed-valence states of rotaxane metal complexes

Research Project

Project/Area Number 13640562
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

HIGUCHI Seiichiro  Faculty of Education, Department of Chemistry, Professor, 教育学部, 教授 (20011017)

Co-Investigator(Kenkyū-buntansha) HOSHINO Yoshimasa  Faculty of Education, Department of Chemistry, Assoc. Professor, 教育学部, 助教授 (50219177)
Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2002: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 2001: ¥2,700,000 (Direct Cost: ¥2,700,000)
Keywordsmixed-valence complexes / ruthenium complexes / rotaxane complexes / alkyne / cumulene / spectroelectrochemistry / cyclodextrin / oxalato complexes / 混合原子価状態 / 二核錯体 / ポリイン系スペーサー / 電気化学
Research Abstract

(1) Tow novel mononuclear (β-diketonato)ruthenium(III) complexes with long conjugated chain composed of alternative ethynyl and aromatic groups at 3-carbon in 2, 4-pentandionato chelate have been prepared.
Furthermore, two novel binuclear (β-diketonato)ruthenium(III) complexes have been prepared by oxidative coupling reactions of the ethynyl groups in the novel mononuclear complexes. Reaction of the oxidative coupling in the presence of cyclodextrin gave unidentified ruthenium species which exhibited visible spectrum similar to the corresponding binuclear complexes.
(2) The binuclear ruthenium complexes with the alternative spacers exhibited two overlapping one-electron oxidation and reduction steps on the cyclic voltammograms. The two oxidation and reduction steps can be assigned to the oxidation of ruthenium(III) to ruthenium(IV) and to the reduction of ruthenium(III) to ruthenium(II), respectively. These results indicate that electrochemical interactions between metals in the Ru^<IV>- … More Ru^<III> mixed-valence state of the binuclear complexes with two aromatic rings in the spacer are considerably smaller than that of the corresponding binuclear complexes with only one aromatic ring.
(3) Single crystal structure analysis has been carried out on a butadiynyl bridged (β-diketonato)ruthenium(III) dimmer(1). Strong electronic coupling over 1.3 nm distance has been observed for the one-electron oxidized state. The fully delocalized (Class III mixed-valent) system 1^+ is distinguished by an extremely intense (ε = 25000 mol^<-1> dm^3 cm^<-1>) inter-valence charge transfer (IVCT) band at 1730 nm and a single intense vibrational band at 2078 cm^<-1> associated with contributions from cumulene resonance structures.
(4) A novel oxalate-bridged binuclear ruthenium(III) complex, [{Ru(acac)_2}_2(μ-ox)] (acac^- = acetylacetonate and ox^<2-> = oxalate), has been prepared via self-dimerization of K[Ru(acac)_2(ox)] in aqueous solutions containing ferric salts as catalyst. The Ru^<III>-Ru^<II> mixed-valence species generated electrochemically with K_c = 10^<5.0> for the comproportionation constant exhibits a weak IVCT band at 1430 nm. IR spectra from spectroelectrochemistry indicated a partially localized mixed-valence state. Less

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • Research Products

    (20 results)

All Other

All Publications (20 results)

  • [Publications] Yoshimasa Hoshino: "Molecular Design for Long-Range Electronic Communication between Metals"Platinum Metals Review. 45(1). 2-11 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Li-Yan Wang: "Synthesis, Structure, and Preliminary Magnetic Studies of a Cluster Polymer with a Hexacopper(II) Barrel Portion"Chemistry Letters. 32(2). 202-203 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yoshimasa Hoshino: "Long-Range Electronic Coupling in Various Oxidation States of a C_4-Linked Tris(β-diketonato)ruthenium Dimer"Angewandte Chemie International Edition. 42(6). 674-677 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Taku Fujino: "Synthesis and Spectroelectrochemical Characterization of a Novel Oxalate-Bridged Binuclear Ruthenium(III) Complex"Chemistry Letters. 32(3). 274-275 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Li-Yan Wang: "Synthesis, Structure, and Preliminary Magnetic Studies of Unprecedented Hexacopper(II) Barrel Clusters with Spin Ground State S=3"Dalton Transaction. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Taku Fujino: "Preparation, structures and properties of oxalate-bridged binuclear iron(III) complex : [(acac)_2Fe(μ-ox)Fe(acac)_2] and [(acac)_2Fe(μ-ox)Fe(acac)_2]・CH_2ClCH_2Cl"Inorganica Chimica Acta. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yoshimasa Hoshino: "Synthesis and Characterization of Mixed-ligand Ruthenium(III) Complexes with Oxalate and Acetylacetonate Ions"Inorganica Chimica Acta. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yoshimasa Hoshino: "Molecular Design for Long-Range Electronic Communication between Metals. Evaluation of polyyne and ethynylated aromatic systems as molecular wires using binuclear ruthenium β-diketone complexes"Platinum Metals Review. 45, No.1. 2-11 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yoshimasa Hoshino, Seiichiro Higuchi, Jan Fiedler, Cheng-Yong Su, Axel Knodler, Brigitte Schwederski, Biprajit Sarkar, Heiko Hartmann, Wolfgang Kaim: "Long-Range Electronic Coupling in Various Oxidation States of a C_4-Linked Tris(β-diketonato)ruthenium Dimer"Angewandte Chemie International Edition. 42, No.6. 674-677 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Li-Yan Wan, Satoshi Igarashi, Yasuhiko Yukawa, Takeshi Hashimoto, Kunio Shimizu, Yoshimasa Hoshino, Andrew Harrison, Guillem Aromi, Richard E.P.Winpenny: "Synthesis, Structure, and Preliminary Magnetic Studies of a Cluster Polymer with a Hexacopper(II) Barrel Portion"Chemistry Letters. 32, No.2. 202-203 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Taku Fujino, Yoshimasa Hoshino, Motoki Eto, Yasuhiko Yukawa, Jan Fiedler, and Wolfgang Kaim: "Synthesis and Spectroelectrochemical Characterization of a Novel Oxalate-Bridged Binuclear Ruthenium(III) Complex"Chemistry Letters. 32, No.3. 274-275 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Li-Yan Wang, Satoshi Igarashi, Yasuhiko Yukawa, Yoshimasa Hoshino, Olivier Roubeau, Guillem Aromi and Richard E.P.Winpenny: "Synthesis, Structure, and Preliminary Magnetic Studies of Unprecedented Hexacopper(II) Barrel Clusters with Spin Ground State S = 3"Dalton Transaction. in press. (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Taku Fujino, Yoshimasa Hoshino, Satoshi Igarashi, Yoshio Masuda, and Yasuhiko Yukawa: "Preparation, Structures and Properties of Oxalate-bridged Binuclear Iron(III) Complex : [(acac)_2Fe(μ-ox)Fe(acac)_2] and [(acac)_2Fe(μ-ox)Fe(acac)_2]・CH_2ClCH_2Cl"Inorganics Chimicas Acta. in press.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yoshimasa Hoshino, Motoki Eto, Taku Fujino, Yasuhiko Yukawa, Tetsuo Ohta, Akira Endo, Kunio Shimizu, and G.P.Sato: "Synthesis and Characterization of Mixed-ligand Ruthenium(lll) Complexes with Oxalate and Acetylacetonate Ions"Inorganics Chimicas Acta. in press.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 星野 由雅: "Molecular Design for Long-Range Electronic Communication between Metals"Platinum Metals Review. 45(1). 2-11 (2001)

    • Related Report
      2002 Annual Research Report
  • [Publications] Li-Yan Wang: "Sysnthesis, Structure, and Preliminary Magnetic Studies of a Cluster Polymer with a Hexacopper(II) Barrel Portion"Chemistry Letters. 32(2). 202-203 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 星野 由雅: "Long-Range Electronic Coupling in Various Oxidation States of a C_4-Linked Tris(β-diketonato) ruthenium Dimer"Angewandte Chemie International Edition. 41(6). 674-677 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 藤野 拓: "Synthesis and Spectroelectrochemical Characterization of a Novel Oxalate-Bridged Binuclear Ruthenium(III) Complex"Chemistry Letters. 32(3). 274-275 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Li-Yan Wang: "Synthesis, Structure, and Preliminary Magnetic Studies of Unprecedented Hexacopper(II) Barrel Clusters with Spin Ground State S=3"Dalton Transaction. (発表予定).

    • Related Report
      2002 Annual Research Report
  • [Publications] 藤野 拓: "Preparation, structures and properties of oxalate-bridged binuclear iron(III) complex : [(acac)_2Fe(μ-ox)Fe(acac)_2 and [(acac)_2Fe(μ-ox)Fe(acac)_2]・CH_2ClCH_2Cl"Inorganica Chimica Acta. (発表予定).

    • Related Report
      2002 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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