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1999 Fiscal Year Final Research Report Summary

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
KeywordsTetranuclear Complex / Manganese Complex / Copper Complex / Photo-induced Oxidation / X-ray Crystallography / dimmer-of-dimmers / Magnetic Susceptibility
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.

  • Research Products

    (30 results)

All Other

All Publications (30 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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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

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Published: 2001-10-23  

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