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Studies on Magnetic Properties of Transition Metal Polynuclear Complexes and Molecular Design Aiming to Single-Molecule Magnets

Research Project

Project/Area Number 14540533
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 機能・物性・材料
Research InstitutionOsaka University

Principal Investigator

NAKANO Motohiro  Osaka University, Graduate School of Engineering, Lecturer, 大学院・工学研究科, 講師 (00212093)

Project Period (FY) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2003: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2002: ¥2,600,000 (Direct Cost: ¥2,600,000)
Keywordssingle-molecule magnet / polynuclear complex / magnetic susceptibility / magnetic anisotropy / non-collinear magnetism / Spin-crossover complex / dielectric constant / Jahn-Teller effect
Research Abstract

1.Relaxation Mechanism of Single-Chain Magnets
Single-Chain Magnets (SCMs) are a class of quantum magnets, recently developed from Single-Molecule Magnets (SMMs). We proposed a novel mechanism of relaxation processes in SCMs based on a spin-vector model characterized by an intrachain ferromagnetic interaction J along with a single-ion anisotropy D. This model can be applied to a wide range of SCM systems from a SMM limit J/D 0 of isolated molecule to a Glauber-dynamics limit J/D >> 1 for a pure Ising chain. It is an excellent feature of the model that it provides a rational account for a "barrier-height crossover" observed in some ferromagnetic SCMs as a crossover of dominant relaxation process from a single-spin flip to a two-spin cluster flip possessing different activation barriers.
2.Critical Phenomena of Spin-Crossover Complex [Mn(taa)]
Spin-crossover complex [Mn(taa)] is known as a unique system showing a dielectric response in addition to an optically-controllable spin bistability. In order to clarify intermolecular interactions responsible to the phase transition in [Mn(taa)] crystals, we prepared some mixed-crystals with [Ga(taa)], a diamagnetic analogue of the Mn complex with the isomorphous crystal structure. A T-x phase diagram of [Mn_xGa_<1-x>(taa)] determined by magnetic and dielectric measurements revealed a critical phenomenon switching from a first-order phase transition to a spin-equilibrium behavior. The suppression of the spin-crossover phase transition made it possible to estimate the energy barrier for pseudo-rotation of an [Mn(taa)] molecule.
3.Development of Computer Programs for Magnetization Analysis
Some computer codes were developed to analyze magnetization curves and HF-EPR results of SMMs. Among them a code implementing the ligand-field theoretical approach was especially effective to elucidate magnetic properties of SMMs including Co(II) ions, which were difficult to be treated by conventional spin-Hamiltonian approach.

Report

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

    (25 results)

All Other

All Publications (25 results)

  • [Publications] M.Nakano et al.: "Dynamic Jahn-Teller character of mananese(III) spin-crossover complex [Mn(taa)] (H_3taa = tris(1-(2-azolyl)-2-azabuten-4-yl)amine)"ADVANCES IN QUANTUM CHEMISTRY. 44. 617-630 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kawabata et al.: "Crystal structures of [Rh(η^5-C_5H_5)(C_3S_5)] and [Rh(η^5-C_5Me_5)(C_3S_5)]_2 and properties of their oxidized species"JOURNAL OF ORGANOMETALLIC CHEMISTRY. 689(2). 405-410 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kubo et al.: "X-ray crystal structure and electrical conductivity of [Au(ppy)(C_8H_4S_8)]_2[PF_6]"EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. 2003(22). 4093-4098 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Hashiguchi et al.: "Heat capacities of quasi-two-dimensional hetero-spin honeycomb magnets {NBu_4[(CuCr^<III>)-Cr^<II>(ox)_3]}_n and {PPh_4[(MnCr^<III>)-Cr^<II>(ox)_3]}_n : High-temperature series ex"JOURNAL OF CHEMICAL PHYSICS. 119(13). 6856-6867 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] A.Yamaguchi et al.: "Nonexponential magnetization relaxation in a manganese single-molecule magnet"PHYSICA B-CONDENSED MATTER. 329(2). 1174-1175 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Oshio et al.: "High-spin wheel of a heptanuclear mixed-valent Fe-II, Fe-III complex"ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 42(2). 223 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kawabata et al.: "Properties of organometallic sulfur-rich dithiolate complexes [M(L)(C_8H_4S_8)] (M = Rh^<III> and Ir^<III>;L = η^5-C_5H_5 and η^5-C_5Me_5) and their oxidation"European Journal of Inorganic Chemistry. Vol.2004. 4093-4098 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kawabata et al.: "Crystal structures of [Rh(η^5-C_5H_5)(C_3S_5)] and [Rh(η^5-C_5Me_5)(C_3S_5)]_2 and properties of their oxidized species"Journal of Organometallic Chemistry. Vol.689. 405-410 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Nakano et al.: "Dynamic Jahn-Teller character of mananese(III) spin-crossover complex (Mn(taa)] (H_3taa = tris(1-(2-azolyl)-2-azabuten-4-yl) amine)"Advances in Quantum Chemistry. Vol.44. 617-630 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kubo et al.: "X-ray crystal structure and electrical conductivity of [Au(ppy)(C_8H_4S_8)]_2[PF_6]"European journal of Inorganic Chemistry. Vol.2003. 4093-4098 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Hashiguchi et al.: "Heat capacities of quasi-two-dimensional hetero-spin honeycomb magnets {NBu_4[(CuCr^<III>)-Cr^<II>(ox)_3] }_n and { PPh_4[(MnCr^<III>)-Cr^<II>(ox)_3]}_n : High-temperature series expansion analysis"Journal of Chemical Physics. Vol.119. 6856-6867 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] A.Yamaguchi et al.: "Nonexponential magnetization relaxation in a manganese single-molecule magnet"Physica B-Condensed Matter. Vol.329. 1174-1175 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Oshio et al.: "High-spin wheel of a heptanuclear mixed-valent Fe-II, Fe-III complex"Angewandte Chemie-International Edition English. Vol.42. 223-225 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Nagano et al.: "Strain energy of phenanthrene"Journal of Chemical Thermodynamics. Vol.35. 1403-1412 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kubo et al.: "Preparation and oxidation of polarized Au(III) complexes having both the C-deprotonated-2-phenylpyridine (ppy) and a sulfur-rich dithiolate ligand and X-ray crystal structure of [Au(η^2-C, N-ppy)(η^2-S, S-C_8H_4S_8)] ・O.5DMF"Journal of Organometallic Chemistry. Vol.669. 141-148 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kubo et al.: "Oxidation of cobalt(III)-sulfur-rich dithiolate complexes and spectroscopic and electrical properties of the oxidized species"Inorganica Chimica Acta. Vol.346. 43-48 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] E.-C.Yang et al.: "Exchange bias in Ni_4 single-molecule magnets"Polyhedron. Vol.22. 1727-1733 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Nakano et al.: "Dielectric behavior of manganese(III) spin-crossover complex [Mn(taa)]"Physical Review B. Vol.66. article no.212412 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Nakano et al.: "Dynamic Jahn-Teller character of mananese(III) spin-crossover complex [Mn(taa)] (H_3taa = tris(1-(2-azolyl)-2-azabuten4-yl)amine)"ADVANCES IN QUANTUM CHEMISTRY. 44. 617-630 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Kawabata et al.: "Crystal structures of [Rh(η^5-C_5H_5)(C_3S_5)] and [Rh(η^5-C_5Me_5)(C_3S_5)]_2 and properties of their oxidized species"JOURNAL OF ORGANOMETALLIC CHEMISTRY. 689(2). 405-410 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Kubo et al.: "X-ray crystal structure and electrical conductivity of [Au(ppy)(C_8H_4S_8)]_2[PF_6]"EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. 2003(22). 4093-4098 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Hashiguchi et al.: "Heat capacities of quasi-two-dimensional hetero-spin honeycomb magnets {NBu_4[(CuCr^<III>)-Cr^<II>(ox)_3]}_n and {PPh_4[(MnCr^<III>)-Cr^<II>(ox)_3]}_n : High-temperature series ex"JOURNAL OF CHEMICAL PHYSICS. 119(13). 6856-6867 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] A.Yamaguchi et al.: "Nonexponential magnetization relaxation in a manganese single-molecule magnet"PHYSICA B-CONDENSED MATTER. 329(2). 1174-1175 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Oshio et al.: "High-spin wheel of a heptanuclear mixed-valent Fe-II, Fe-III complex"ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 42(2). 223 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 中野 元裕: "Dielectric behavior of manganese(III)spin-crossover complex[Mn(taa)]"Physical Review B. 66. 212412 (2003)

    • Related Report
      2002 Annual Research Report

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

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