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Studies on Magneto-Photo Multifunctional System of Polynuclear Complexes Comprised by Discrete Metal Complexes

Research Project

Project/Area Number 10440196
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

TOKII Tadashi  Saga University, Faculty of Science and Engineering, Professor, 理工学部, 教授 (40039269)

Co-Investigator(Kenkyū-buntansha) KOIKAWA Masayuki  Saga University, Faculty of Science and Engineering, Lecturer, 理工学部, 講師 (90221952)
Project Period (FY) 1998 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥9,300,000 (Direct Cost: ¥9,300,000)
Fiscal Year 1999: ¥3,800,000 (Direct Cost: ¥3,800,000)
Fiscal Year 1998: ¥5,500,000 (Direct Cost: ¥5,500,000)
KeywordsTetranuclear Complex / Manganese Complex / Copper Complex / Photo-induced Oxidation / X-ray Crystallography / dimmer-of-dimmers / Magnetic Susceptibility / 三座配位子 / 四該銅錯体
Research Abstract

A tetranuclear manganese(II,III) complex, [MnィイD22ィエD2(O)(PhィイD22ィエD2MeCCOO)(phen)ィイD22ィエD2]ィイD22ィエD2(PFィイD26ィエD2)ィイD22ィエD2 (2), has been assembled from a binuclear manganese(II) complex, [Mn(PhィイD22ィエD2MeCCOO)(phen)ィイD22ィエD2]ィイD22ィエD2(PFィイD26ィエD2)ィイD22ィエD2 (1) by use of a photo-induced oxidation reaction. Tetranuclear core in 2 consists of two μ-oxo-bis(μ-carboxylato)dimanganese units making a dimmer-of-dimers structure. The valence of the central and the terminal manganese atoms are assigned to +3 and +2, respectively. The core structure is stabilized by μィイD23ィエD2-oxo bridgeing and p-p stacking of phen as a terminal ligand. The oxidation reaction of 1 in a methanol/acetonitrile solution has been investigated by means of a photo-irradiation procedure using a super high-pressure mercury lamp. The solution gradually changes from yellow to dark brown, and a new intense absorption band appears at about 20x10ィイD13ィエD1cmィイD1-1ィエD1 with the passage of irradiation.
Tetracopper complexes [CuL2H]ィイD24ィエD2 (3), [CuL2Me]ィイD24ィエD2 (4), and [CuL2Cl]ィイD24ィエD2 (5) with a reduced Schiff base type tridentate ligand HィイD22ィエD2L2X (X = H, 4-Me, 4-Cl) were prepared and characterized by elemental analyses and magnetic measurements. The crystal structure of 1 was determined by X-ray crystallography. Tetracopper core is represented as a dimer-of-dimers structure by the stacking of two dicopper nits bridged by alcoholic oxygens. Magnetic behaviors of the complexes are explained by modified equation based on the theoretical Spin Hamiltonian. The exchange integrals (-2J) are evaluated at 292μ 366 cmィイD1-1ィエD1 for SP dicopper cores and 104 - 120 cmィイD1-1ィエD1 for TBP, respectively, indicating the existence of different type of antiferromagnetic interaction-pathways corresponded to each copper geometry.

Report

(3 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • Research Products

    (38 results)

All Other

All Publications (38 results)

  • [Publications] Mohammad Yeamin Reza: "Synthesis and Crystal Structure of a Novel Hexanuclear Zr(IV) Complex with Hydoroxo and Carboxylato Bridging"Bulltin of the Chemcal Society of Japan. 71. 155-160 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Kani: "A dimeric Copper(II) 4-Chlorophenoxy-isobutyrate Adduct with Methanol and a Monomeric Copper(II) 4-Chlorophenoxy-isobutyrate Adduct with Pyridine"Acta Crystallogr.. C54. 193-195 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Masayuki Koikawa: "Syntheses and Crystal Structures of divalent Complexes with a New Hexadentate Ligand Derived from 1,4,7-Triazacyclononane"Journal of Chemical Society. Dalton Transaction. 1085-1086 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Masayuki Koikawa: "Crystal Structure and Characterization of Binuclear Copper(II) Complex with N-(2-hydroxyphenyl)-3-methoxycarbonyl-4,6,-dimethylsalicylamide"Inorganica Chimica Acta. 277. 134-137 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Mohammad Yeamin Reza: "Synthesis and Crystal Structure of a NovelHexanuclear Zr(IV) Complexewith 1,10-Phenanthroline Including Carboxylato, Hydroxo, and Oxo Bridging"Polyhedron. 18. 787-792 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Shouichi Tomida: "Assembly of a Tetranuclear Mixed-Valence monganese(II. III) Complex from a Binuclear Manganese (II) Complex by Photo-Irrediation"Chemistry Letters. 437-438 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Kani: "A Dimeric Copper(II) Bis(4-chlorophenoxy)acetate Adduct with Dimethylformamide"Acta Crystallogr.. C55. 316-318 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Hideaki Matsushima: "Structural Charactrization and Magnetic Properties of Triply Carboxylato-Bridged Dinuclear Copper(II) Complexes"Bulltin of Chemical Society Japan. 72. 1025-1035 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Hideki Furutachi: "Fe^<II>Pb^<II> and Fe^<III> Complexes of Macrocyclic Compartmental Ligands; Different Cyclization in Stepwise Template synthesis using Fe^<II>/Pb^<II> or Fe^<III>/Pb^<II> pairs"Journal of Chemical Society, Dalton Transaction. 367-372 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H. matsushima: "Magnetic properties and Crystal structure of Bis(μ-pyrazolato)bridged Dicopper(II,II) Complexes with 1,10-Phenanthroline or 2,2'-Bipyridine"Journal of Chemical Society, Dalton Transaction. 971-977 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S. Nishino: "Selective Dioxygenation of Cyclohexane Catalysed by Hydrogen Peroxde and Dinuclear Iron(III) Complexes with μ-Alkoxo Bridges"Journal of Chemical Society, Dalton Transaction. 1509-1513 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H. Nakagawa: "A Monomeric and a Dimeric Copper(II) Trigonelline Adduct with Chloride, and a Dimeric Copper(II) 1-Methyl-2-pyrrolecarboxylate Adduct with 3-Methylpyridine"Acta Crystallographica C. C55. 316-318 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S. Nishino: "interaction between the Peroxide adduct of Binuclear Iron(III) Complex with (HPTP) Anion and the Sugar Moiety of Nucleosides"Z. Naturforsch.. 54b. 1272-1276 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Michio Nakashima: "Synthesis and Structure of Tetrakis carboxylato-Bridged Dinuclear Manganese(II) Quinoline Complexes, with Carboxylates Diphenylacetate and 2,2-Diphenylpropanoate"Chemistry Letters. 1277-1278 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Masahito Kodera: "A Cu(II)-Mediated C-H Oxygenation of Sterically Hindered Tripyridine Ligands To Form Trianggular Cu(II)_3 Complexes"Inorganic Chemistry. 39. 226-234 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Y.Reza, H.Matsushima, M.Koikawa, M.Nakashima and T.Tokii: "Synthesis and Crystal Structure of a Novel Hexanuclear Zr(IV) Complex with Hydroxo and Carboxylato Bridging"Bull. Chem. Soc. Jpn.. 71. 155-160 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y.Kani, S.Ohba, H.Matsushima and T.Tokii: "A dimeric Copper(II) 4-Chlorophenoxy-isobutyrate Adduct with Methanol and a Monomeric Copper(II) 4-Chlorophenoxy- isobutyrate Adduct with Pyridine"Acta Crystallogr. C54. 193-195 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Koikawa, K.B.Jensen, H.Matsushima, T.Tokii and H.Toftlund: "Synthesis and Crystal Structure of Divalent Complexes with a New hexadentate Ligand Derived from 1,4,7-Triazacyclononane"J. Chem. Soc., Dalton Trans.. 1085-1086 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Koikawa, H.Matsushima andT.Tokii: "Crystal Structure and Characterization of Binuclear Copper(II) Complex with N-(2-hydroxyphenyl)-3-methoxycarbonyl-4,6-dimethylsalicylamide"Inorg. Chim. Acta. 277. 134-137 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Y.Reza, H.Matsushima, M.Koikawa, M.Nakashima and T.Tokii: "Synthesis and Crystal Structure of a Novel Hexanuclear Zr(IV) Complex with 1,10-Phenanthroline Including Carboxylato, Hydroxo, and Oxo Bridging"Polyhedron. 18. 787-792 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S.Tomida, H.Matsushima, M.Koikawa, M.Koikawa and T.Tokii: "Assembly of a Tetetranuclear Mixed-Valence Manganese(II,III) Complex from a Binuclear Manganese(II) Complex by Photo-Irradiation"Chem. Lett.. 437-438 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y.kani, M.Tsuchimoto, S.Ohba, H.Matsushima, M.Noguchi and T.Tokii: "A Dimeric Copper(II) Bis(4-chlorophenoxy)acetate Adduct with Dimethylformamide"Acta Crystallogr.. C55. 316-318 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H.Matsushima, M.Koikawa, R.Nukada, M.Mikuriya and T.Tokii: "Structural Characterization and Magnetic Properties of Triply Carboxylato-Bridged Dinuclear Copper(II) Complexes"Bull. Chem. Soc. Jpn.. 72. 1025-1035 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H.Furutachi, A.Ishida, H.Miyasaka, N.Fukita, M.Ohba, H.Okawa and M.Koikawa: "Fe|-D1II-|D1Pb|-D1II-|D1 and Fe|-D1III-|D1 Complexes of Macrocyclic Compartmental Ligands: Different Cyclization in Stepwise template Synthesis using Fe|-D1II-|D1/Pb|-D1II-|D1 or Fe|-D1III-|D1/Pb|-D1II-|D1 pairs"J. Chem. Soc., Dalton Trans.. 367-372 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H.Matsushima, H.Hamada, K.Watanabe, M.Koikawa and T.Tokii: "Magnetic properties and Crystal Structures of Bis(μ-pyrazolato)bridged Dicopper(II,II) Complexes with 1,10-Phenanthroline or 2,2'-Bipyridine"J. Chem. Soc., Dalton Trans.. 971-977 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S.Nishino, H.Hosomi, S.Ohba, H.Matsushima, T.Tokii and Y.Nishida: "Selective Dioxygenation of Cyclohexane catalysed by Hydrogen Peroxide and Dinuclear Iron(III) Complexes with μ-Alkoxo Bridges"J. Chem. Soc., Dalton Trans.. 1509-1513 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H.Nakagawa, Y.Kani, M.Tsuchimoto, S.Ohba, H.Matsushima and T.Tokii: "A Monomeric and a Dimeric Copper(II) Trigonelline Adduct with Chloride, and a Dimeric Copper(II) 1-Methyl-2-pyrrolecarboxylate Adduct with 3-Methylpyridine"Acta Crystallogr.. C55. 882-886 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S.Nishida, M.Kunita, T.Kobayashi, H.Matsushima, T.Tokii and Y.Nishida: "Interaction between the Peroxide Adduct of Binuclear Iron(III) Complex with (HPTP) Anion and the Sugar Moiety of Nucleosides"Z. Naturforsch.. 54b. 1272-1276 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Nakashima, H.Maruo, T.Hata and T.Tokii: "Synthesis and Structure of Tetrakis Carboxylato-Bridged Dinuclear Manganese(II) Quinoline Complexes with Carboxylates Diphenylacetate and 2,2-Diphenylpropanoate"Chem. Lett.. 1277-1278 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Kodera, Y.Tachi, T.Kita, H.Kobushi, Y.Sumi, K.Kano, M.Shiro, M.Koikawa, T.Tokii, M.Ohba and H.Okawa: "A Cu(II)-Mediated C-H Oxygenation of Sterically Hindered Tripyridine Ligands To Form Triangular Cu(II)|-D13-|D1 Complexes"Inorg. Chem.. 39. 226-234 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Shouichi Tomida: "Assembly of a Tetranuclear Mixed-Valence Manganese(II,III) Complex from a Binuclear Manganese(II) Complex by Photo-Irradiation"Chemistry Letters. 437-438 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Hideaki Matsushima: "Structual Characterization and Magnetic Properties of Triply Carboxylato-Bridged Dinuclear Copper(II) Complexes"Bulletin of Chemical Society Japan. 72. 1025-1035 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Michio Nakashima: "Synthesis and Structure of Tetrakis Carboxylato-Bridged Dinuclear Manganese(II) Quinoline Complexes,with Carboxylates Diphenylacetate and 2,2-Diphenylpropanoate"Chemistry Letters. 1277-1278 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Hideki Furutachi: "Fe^<II>Pb^<II> and Fe^<III> Complexes of Macrocyclic Compartmental Ligands: Different Cyclization in Stepwise Template Synthesis using Fe^<II/>Pb^<II> or Fe^<III>/Pb^<II> pairs"Journal of Chemical Society,Dalton Transaction. 367-372 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] S.Nishino: "Selective Dioxygenation of Cyclohexane Catalysed by Hydrogen Peroxide and Dinuclear Iron(III) Complexes with μ-Alkoxo Bridges"Journal of Chemical Society,Dalton Transaction. 1509-1513 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H.Nakagawa: "A Monomeric and a Dimeric Copper(II) Trigonelline Adduct with Chloride,and a Dimeric Copper(II) 1-Methyl-2-pyrrolecarboxylate Adduct with 3-Methylpyridine"Acta Crystallographica C. C55. 316-318 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Masayuki koikawa: "Syntheses and Crystal Structures of divalent complexes with a New hexadentate Ligand Derivcd from 1,4,7-Triazacyclononane" Journal of Chemical Society,Dalton Transaction. 1085-1086 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y.Kani: "A dimeric Copper(II)4-Chlorophenoxy-isobutyrate Adduct with methanol and a monomeric Copper(II)4-Chlorophenoxy-isobutyrate Adduct with Pyridine" Acta crystallogr.C54. 193-195 (1998)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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