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Research on Multifunctional Properties Coupled with Photon and Spin for Transition-Metal Complexes

Research Project

Project/Area Number 10440203
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 機能・物性・材料
Research InstitutionThe University of Tokyo

Principal Investigator

KOJIMA Norimichi  Graduate School of Arts & Sci., Univ. Tokyo, Prof., 大学院・総合文化研究科, 教授 (60149656)

Co-Investigator(Kenkyū-buntansha) KOMATSU Tokutaro  Graduate School of Arts & Sci., Univ. Tokyo, Researcher, 大学院・総合文化研究科, 助手 (50280938)
MATSUSHITA Nobuyuki  Graduate School of Arts & Sci., Univ. Tokyo, Associate Prof., 大学院・総合文化研究科, 助教授 (80219427)
Project Period (FY) 1998 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥12,500,000 (Direct Cost: ¥12,500,000)
Fiscal Year 1999: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 1998: ¥9,500,000 (Direct Cost: ¥9,500,000)
KeywordsSpin-crossover / Mixed-valence / Multifunctionality / Valence transition / Photo-induced effect / Photo-induced phase transition / Soliton / Low-spin high-spin transition
Research Abstract

Transition metal complexes with dィイD14ィエD1-dィイD17ィエD1 configuration have a possibility of spin transition between an low-spin state and a high spin state. Particularly, in the case of mixed-valence complexes whose spin states lie in the spin-crossover region, new types of conjugated phenomena due to spin and charge are expected. From this viewpoint, we have synthesized the mixed valence complex, [(n-CィイD23ィエD2HィイD27ィエD2)ィイD24ィエD2N][FeィイD1IIィエD1FeィイD1IIIィエD1(dto)ィイD23ィエD2](dto = CィイD22ィエD2OィイD22ィエD2SィイD22ィエD2), and have investigated the magnetic properties by means of magnetic susceptibility, magnetization, ESR and ィイD157ィエD1Fe Mossbauer spectroscopy. From the measurements of magnetic susceptibility and magnetization as a function of temperature, [(n-CィイD23ィエD2HィイD27ィエD2)ィイD24ィエD2N][FeィイD1IIィエD1FeィイD1IIIィエD1(dto)ィイD23ィエD2] was found to show the ferromagnetic transition at 6 K and to show the reversible charge transfer phase transition at about 120 K. Moreover, we have investigated the spin transition of [Fe(NHィイD22ィエD2trz)ィイD23ィエD2](RSOィイD23ィエD2)22HィイD22ィエD2O. In the case of [Fe(NHィイD22ィエD2trz)ィイD23ィエD2](CィイD2nィエD2HィイD22n+1ィエD2SOィイD23ィエD2)ィイD22ィエD22HィイD22ィエD2O(n=1-9), the transition temperature becomes higher by about 80 K with increasing the length of alkyl chain of the counter anion, and then it saturated at n > 5. The even-odd effect was observed in the hysteresis width.
In the case of three-dimensional mixed-valence system CsィイD22ィエD2AuィイD22ィエD2XィイD26ィエD2, we have discovered a photo-induced Au valence transition for CsィイD22ィエD2AuィイD22ィエD2BrィイD26ィエD2 under high pressure.

Report

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

    (52 results)

All Other

All Publications (52 results)

  • [Publications] A. Ishikawa, et al.: "A <@D1 35@>D1 CI NQR Study on Cs<@D2 2@>D2[Au<@D1 1@>D1C2][Au<@D1 III@>D1CL<@D2 4@>D2]"Z. Naturforsch... 53a. 590-594 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Matsushita, et al.: "Crystal Structure of Mixed-Valence Gold Compound, Cs<@D2 2@>D2 Au<@D1 I@>D1 Au<@D1 III@>D1 Cl<@D2 6 @>D2 up to 18 Gpa."Rev. High Pressure Sci. Technol... 7. 329-331 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Hashimoto, et al.: "Pressure Induced Structural Phase Transition of LaCrO<@D2 3@>D2"Solid State Commun... 108. 691-694 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Yokoyama, et al.: "Spin-crossover Phase Transition of a Chain Fe(11) Complex Studied by X-Ray-Absorption Fine-Structure Spectroscopy."Phys. Rev. B58. 14238-14244 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] X. J. Liu, et al.: "Electronic Structure of the Gold Complexes Cs<@D2 2@>D2 Au<@D2 2@>D2 X<@D2 6@>D2 (X=I,Br,and CI)."Phys. Rev. B59. 7925-7930 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] X. J. Liu, et al.: "Pressure Induced Phase Transition in Mixed-Valence Gold Complexes Cs<@D2 2@>D2 Au<@D2 2@>D2 X<@D2 6@>D2(X=CI and Br)."J. Chem. Phys... 110. 9174-9178 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Komatsu, et al.: "A Weakly Coupled Molecular Spin-Ladder ( BEDT-TTF)Zn(SCN)<@D2 3@>D2"Synth, Metals,. 103. 1923-1924 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Kojima,et al,: "EXAFS Study on the Spin-Crossover System, [Fe(4-NH<@D2 2@>D2 trz)<@D2 3@>D2](R-SO<@D2 3@>D2)<@D2 2@>D2"Synth, Metals,. 103. 2154-2154 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Murakami, et al.: "Control of Te and Spin Bistability in the Spin-Crossover System, Fe(4-NH<@D2 2@>D2 trz)<@D2 3@>D2](R-SO<@D2 3@>D2)<@D2 2@>D2"Synth. Metals.. 103. 2157-2158 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Takano, et al.: "Photo-Induced and Doping Effects on the Non-linear Excitation in [PtX2(en)][PtX4(en)](X = CI,Br, I)."Synth. Metals.. 103. 2153-2153 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] X. J. Liu, et al.: "Broad Raman Band in the Single -Valence State of Cs<@D2 2@>D2 Au<@D2 2@>D2 X<@D2 6@>D2(X=Cl and Br)."J. Phys. Soc. Jpn... 68. 3134-3137 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] X. J. Liu, et al.: "Photoinduced Phase Transition in a Mixed-Valence Gold Complex."Phys. Rev. B61. 20-23 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] G. Saito, et al.: "Formation of 2:1 Insulating Complexes of D<@D1 =2@>D1 D<@D1+2@>D1 A<@D1 2-@>D1 Alternating Stack and 4:1 Smimetallic Complex Using M(dto)<@D2 2@>D2 Dianions (M= Ni,Pt, Pd and dto:dithiooxalate)."Mol. Cryst. Liq. Cryst.. (in press). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Kojima,et al,: "P-T Phase Diagram and Au Valence State of the Perovskite-type Au Mixed-Valence Complexes M<@D2 2@>D2[Au<@D1 I@>D1 X<@D2 2@>D2][Au<@D1 III@>D1 X<@D2 4@>D2](M=K,Rb,Cs;X=Cl,Br,I)."Coord, Chem. Rev.. (in press). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Kojima,et al,: "Au Valence State and Phaste Diagram in the Gold Mixed-Valence Complexes, M<@D2 2@>D2[Au<@D1I@>D1 X<@D22@>D2][Au<@D1III@>D1X<@D24@>D2](M = Rb,Cs; X = Cl,Br, and I)."Bull, Chem.Soc. Jpn.. (in press). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S. Matsuba, et al.: "Studies of Mixed-Valence States in One-Dimensional Halogen-Bridged Gold Compound [Au<@D1I@>D1X(DBS)][Au<@D1III@>D1X<@D23@>D2(DBS)](X = Cl,Br,I; DBS = dibenzylsulfide)."Mol.Cryst. Liq. Cryst... (in press). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S. Toyazaki, et al.: "Study on the Spin-Crossover System for [Fe(4-NH<@D22@>D2trz)<@D23@>D2] (p-CH<@D23@>D2C<@D26@>D2H<@D24@>D2SO<@D23@>D2)<@D22@>D2 nH<@D22@>D2O."Mol. Cryst. Liq. Cryst.. (in press). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Komatsu, et al.: "Molecular-Orbital Calculation on the Neutral Mixed-Valent Platinum Complex [Pt<@D1I@>D1ICl<@D22@>D2(en)][Pt<@D1IV@>D1Cl<@D24@>D2(en)]."Mol. Cryst. Liq. Cryst.. (in press). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S. Sugano and N. Kojima: "Magneto Optics"Springer. 334 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Ishikawa, et al.: "A ィイD135ィエD1Cl NQR Study on CsィイD22ィエD2[AuィイD1IィエD1ClィイD22ィエD2][AuィイD1IIIィエD1ClィイD24ィエD2]."Z. Naturforsch.. 53a. 590-294 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Matsushita, et al.: "Crystal Structure of Mixed-Valence Gold Compound, CsィイD22ィエD2AuィイD11ィエD1AuィイD1IIIィエD1ClィイD26ィエD2 up to 18 GPa."Rev. High Pressure Sci. Technol.. 7. 329-331 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Hashimoto, et al.: "Pressure Induced Structural Phase Transition of LaCrOィイD23ィエD2."Solid State Commun.. 108. 691-694 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Yokoyama, et al.: "Spin-crossover Phase Transition of a Chain Fe (II) Complex Studied by X-Ray-Absorption Fine-Structure Spectroscopy."Phys. Rev.. B58. 14238-14244 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] X. J. Liu, et al.: "Electronic Structure of the Gold Complexes CsィイD22ィエD2AuィイD22ィエD2XィイD26ィエD2 (X=I, Br, and Cl)."Phys. Rev.. B59. 7925-7930 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] X. J. Liu, et al.: "Pressure Induced Phase Transition in Mixed-Valence Gold Complexes CsィイD22ィエD2AuィイD22ィエD2XィイD26ィエD2(X=Cl and Br)."J. Chem. Phys.. 110. 9174-9178 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Komatsu, et al.: "A Weakly Coupled Molecular Spin-Ladder (BEDT-TTF)Zn(SCN)ィイD23ィエD2."Synth. Metals. 103. 1923-1924 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Kojima, et al.: "EXAFS Study on the Spin-Crossover System, [Fe(4-NHィイD22ィエD2trz)ィイD23ィエD2](R-S0ィイD23ィエD2)ィイD22ィエD2."Synth. Metals. 103. 2154 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Murakami, et al.: "Control of Tc and Spin Bistability in the Spin-Crossover System, Fe(4-NHィイD22ィエD2trz)ィイD23ィエD2](R-S0ィイD23ィエD2)ィイD22ィエD2."Synth. Metals. 103. 2157-2158 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Takano, et al.: "Photo-Induced and Doping Effects on the Non-linear Excitation in [PtX2(en)][PtX4(en)](X = Cl, Br, I)."Synth. Metals. 103. 2153 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] X. J. Liu, et al.: "Broad Raman Band in the Single-Valence State of CsィイD22ィエD2AuィイD22ィエD2XィイD26ィエD2(X=Cl and Br)."J. Phys. Soc. Jpn.. 68. 3134-3137 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] X. J. Liu, et al.: "Photoinduced Phase Transition in a Mixed-Valence Gold Complex."Phys. Rev.. B61. 20-23 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] G. Saito, et al.: "Formation of 2 : 1 Insulating Complexes of DィイD1+ィエD1 DィイD1+ィエD1 AィイD12-ィエD1 Alternating Stack and 4 : 1 Semimetallic Complex Using M(dto)ィイD22ィエD2Diarrions (M=Ni, Pt, Pd and dto : dithiooxalate)"Mol. Cryst. Liq. Cryst.. (in press). (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Kojima, et al.: "P-T Phase Diagram and Au Valence State of the Perovskite-type Au Mixed-Valence Complexes MィイD22ィエD2[AuィイD1IィエD1XィイD22ィエD2][AuィイD1IIIィエD1XィイD24ィエD2](M=K, Rb, Cs ; X=Cl, Br, I)"Coord. Chem. Rev.. (in press). (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Kojima: "Au Valence St6ate and Phase Diagram in the Gold Mixed-Valence Complexes, MィイD22ィエD2[AuィイD1IィエD1XィイD22ィエD2][AuィイD1IIIィエD1XィイD24ィエD2](M = Rb, Cs ; X = Cl, Br, and I)."Bull. Chem. Soc. Jpn.. 73 (in press). (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S. Matsuba, et al.: "Studies of Mixed-Valence States in One-Dimensional Halogen-Bridged Gold Compounds [AuィイD1IィエD1X(DBS)][AuィイD1IIIィエD1XィイD23ィエD2(DBS)](X = Cl, Br, I ; DBS = dibenzylsulfide)"Mol. Cryst. Liq. Cryst.. (in press). (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S. Toyazaki, et al.: "Study on the Spin-Crossover System for [Fe(4-NHィイD22ィエD2trz)ィイD23ィエD2] (p-CHィイD23ィエD2CィイD26ィエD2HィイD24ィエD2S0ィイD23ィエD2)ィイD22ィエD2 nHィイD22ィエD20."Mol. Clyst. Liq. Cryst.. (in press). (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Komatsu, et al.: "Molecular-Orbital Calculation on the Neutral Mixed-Valent Platinum Complex [PtィイD1IィエD1IClィイD22ィエD2(en)][PtィイD1IVィエD1ClィイD24ィエD2(en)]."Mol. Clyst. Liq. Cryst.. (in press). (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Kojima: "Elementary Excitations in Magneticall Ordered Materials""Magneto Optics" ed. by S. Sugano and N. Kojima. (Springer). 35-73 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y.Murakami,N.Kojima,et al.: "Control of Tc and Spin Bistability in the Spin-Crossover System. [Fe(4-NH_2trz)_3 ](R-SO_3)_2"Syntetic Metals. 103. 2157-2158 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Kojima,Y.Murakami,et al.: "EXAFS Study on the Spin-Crossover System, [Fe(4-NH_2trz)_3 ](R-SO_3)_2"Syntetic Metals. 103. 2154-2154 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] X.Liu,N.Kojima,et al.: "Electronic Structure of the Gold Complexes Cs_2Au_2X_6(X=I, Br, and Cl)"Physical Review. B59. 7925-7930 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] X.Liu,N.Kojima,et al.: "Pressure Induced Phase Transition in Mixed-Valence Gold Complexes Cs_2Au_2X_6(X=Cl and Br)."J.Chemical Physics. 110. 9174-9178 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Komatsu,N.Kojima,et al.: "A weakly Coupled Molecular Spin-Ladder (BEDT-TTF)Zn(SCN)_3"Synthetic Metals. 103. 1923-1024 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] X.Liu,N.Kojima,et al.: "Photoinduced Phase Transition in a Mixed-valence Gold Complex"Physical Review. B61. 20-23 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] S.Sugino,N.Kojima: "Magneto Optics"Springer. 334 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] A.Ishikawa, N.Kojima, et al.: "A ^<35>Cl NQR Study on Cs_2〔Au^1Cl_2〕〔Au^<111>Cl_4〕." Z.Naturforschung. 53a. 590-594 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Matsushita, N.Kojima, et al.: "Crystal Structure of Mixed-Valence Gold Compound, Cs_2Au^1Au^<111>Cl_6 up to 18 GPa." Rev.High Pressure Science and Technology. 7. 329-331 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Hashimoto, N.Kojima, et al.: "Pressure-Induced Structural Phase Transition of LaCrO_3." Solid State Commun.108. 691-694 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Yokoyama, N.Kojima, et al.: "Spin-Crossover Phase Transition of a Chain Fe(II) Complex Studied by X-Ray-Absorption Fine-Structure Spectroscopy." Physical Review. B58. 14238-14244 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] X.J.Liu, N.Kojima, et al.: "Pressure-Induced Phase Transition in Mixed-Valence Gold Complexes Cs_2Au_2X_6 (X=Cl and Br)." J.Chemical Physics. 110. (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] X.J.Liu, N.Kojima, et al.: "Electronic Structures of Gold Complexes; Cs_2Au_2X_6 (X=I, Br and Cl)." Physical Review. B59. (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] 小島憲道,他10名: "新しい配位子場の科学" (田辺行人監修,講談社), 276 (1998)

    • Related Report
      1998 Annual Research Report

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

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