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Study on the Unusual Electrical Properties of Charge-Transfer Complexes with Intermolecular Hydrogen-Bonds

Research Project

Project/Area Number 07454181
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 InstitutionHOKKAIDO UNIVERSITY

Principal Investigator

INABE Tamotsu  Hokkaido Univ., Grad.School of Sci., Professor, 大学院理学研究科, 教授 (20168412)

Co-Investigator(Kenkyū-buntansha) NAITO Toshio  Hokkaido Univ., Grad.School of Sci., Lecturer, 大学院理学研究科, 講師 (20227713)
Project Period (FY) 1995 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥8,000,000 (Direct Cost: ¥8,000,000)
Fiscal Year 1997: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1996: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1995: ¥5,700,000 (Direct Cost: ¥5,700,000)
KeywordsCharge-Transfer Complexes / Hydrogen-Bonds / 1.6-Diaminopyrene / Electrical Conductivity
Research Abstract

In this research project, systematic crystal growth of 1,6-diaminopyrene (DAP) charge-transfer complexes has been carried out to study on their crystal structures and physical properties. Fifteen electron acceptors, of which acceptor strength distributes in a wide renge, were selected to combine with DAP.These complexes can be categorized into two groups from their structure and electronic state, as follows.
1. Complexes with Neutral Mixed-Stack Structure : The complex with p-chloranil (CHL) belongs to the first group. The crystal comprises mixed-stack columns of neutral donors and acceptors. In general, the electrical conductivity of such a crystal is expected to be very poor. However, it has been found that the complexes with not only CHL but also p-bromanil and 2,5-dibromo-3,6-dichloro-p-benzoquinone shows high conductivity. Furthermore, it has been found that there are two distinguishable trends in their electrical conductiviity and temperature dependence of the magnetic susceptibil … More ity.
2. Complexes with Ionic Segregated-Stack Structure : We have found new five complexes which have ionic segregated-stack structure similar to DAP-TCNQ.In all the complexes, component molecules are completely ionized. The electrical resistivities are quite low ; 10^<-1>-10^3 OMEGA cm at room temperature. However, the activation energies of conduction are extremely large. Though the interplanar spacing between the molecules is uniform, they are suggested to be a spin-Peierls system, since totally symmetric vibrational modes have been observed.
A common characteristic in these two groups is hydrogen-bonds between donors and acceptors. Since rather small anisotropy of the conduction has been found, it has been suggested that the hydrogen-bonding plays some important role in their unusual transport mechanism. Systematic comparison has not been complete due to lack of some structural data. The systematic study on the interaction between the pi-electron systems and the relation with the hydrogen-bonding will be performed after completion of the structure analyzes. Less

Report

(4 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • 1995 Annual Research Report
  • Research Products

    (53 results)

All Other

All Publications (53 results)

  • [Publications] 朝日秀眞、他: "Novel Conducting Charge-Transfer Complexes of 1,4,5,8-Naphthalenetetrone (NTO) and 1,4,9,10-anthracenetetrone (ATO)" Synthetic Metals. 70. 1117-1118 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 武田 定、他: "ESR Study on the Charge Transfer Complexes of N-Salicylideneanilines Containing NHO Hydrogen Bond as a Dynamic Function" Synthetic Metals. 70. 1211-1212 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 関川太郎、他: "Mid-Gap State of the Quasi-One-Dimensional Mott-Hubbard System : Charge Transfer Complex Composed of 1,6-Pyrenediamine and Tetracyanoquinodimethane (DAP-TCNQ)" Synthetic Metals. 70. 1213-1214 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 後藤裕利、他: "High-Resistance Phase and Low-Resistance Phase in 1,6-Diaminopyrene-p-Chloranil (DAP-CHL)" Synthetic Metals. 70. 1237-1238 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 川俣 純、他: "Sallient Nonlinear Optical Properties of Novel Organic Crystals Comprising π-Conjugated Ketones" Applied Physics Letters. 66. 3102-3104 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 森本和弘、他: "Conducting Neutral Radical Crystals of Axially Substituted Phthalocyanine : Crystal Structures, Dimensionality, and Electrical Conductivity" Journal of Materials Chemistry. 5. 1749-1752 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 後藤裕利、他: "Crystal Structure and Physical Properties of 1,6-Diaminopyrene p-Chloranil (DAP-CHL) Charge-Transfer Complex. Two Polymorphs and their Unusual Electrical Properties" Bulletin of the Chemical Society of Japan. 69. 85-93 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 川俣 純、他: "Large Second-Harmonic Generation Coefficients of Bis (benzylidene) cycloalkanones Estimated by the Second-Harmonic Wave Generated with the Evanescent Wave Technique" Chemical Physics Letters. 249. 29-34 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 稲辺 保、他: "Two-Dimensional Molecular Arrangement in Phthalocyanine Based Conducting Crystals" Molecular crystals and Liquid Crystals. 278. 151-156 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 川俣 純、他: "Prominent Second-Order Nonlinear Optical Properties of Novel Ketone Derivatives" Molecular Crystals and Liquid Crystals. 278. 117-124 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 稲辺 保、他: "Unusual Electrical Properties of 1,6-Diaminopyrene Charge-Transfer Complex Crystals" Molecular Crystals and Liquid Crystals. 284. 283-290 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 森本和弘、他: "Molecular Conductors Based on Axially Substituted Phthalocyanine Neutral Radicals" Molecular Crystals and Liquid Crystals. 284. 291-300 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 稲辺 保、他: "Dimensionality Control of Phthalocyanine Based Conductors" Molecular Crystals and Liquid Crystals. 285. 107-112 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 関川太郎、他: "Femtosecond Fluorescence Study of the Substitution Effect on the Proton Transfer in Thermochromic Salicylideneaniline Crystals" Journal of Physical Chemistry A. 101. 644-649 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 関川太郎、他: "Spin-0 Soliton Formation in Spin-Peierls Systems : Charge-Transfer Complexes DAP-TCNQ and DAP-DMTCNQ" Physical Review B. 55. 4182-4190 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 稲辺 保、他: "Wide Variety of Dimensionality in Phthalocyanine Based Molecular Conductors" Synthetic Metals. 86. 1799-1800 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 芥川智行、他: "Crystal Structure and Electrical Conductivity of [NH_4^+][18-crown-6][Ni(dmit)_2]_3" Synthetic Metals. 86. 1861-1862 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 藤縄 祐、他: "Unusual Electrical Properties of 1:1 Charge-Transfer Complexes Composed of 1,6-Diaminopyrene and Some Tetrahalo-p-benzoquinone" Synthetic Metals. 86. 1865-1866 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 伊藤英輔、他: "Soft X-ray Absorption and X-ray Photoelectron Spectroscopic Study of Tautomerism in Intramolecular Hydrogen Bonds of N-Salicylideneaniline Derivatives" Journal of the American Chemical Society. 119. 6336-6344 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 小林孝嘉、他: "Femtosecond Luminescence Study of Hydrogen-Atom-Transfer Processin Thermochromic Crystalline Salicylideneanilines" Journal of Luminescence. 72-74. 508-510 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 大塚岳夫、他: "Crystal Structures and Magnetic Properties of Acid-Base Molecular Complexes, (p-Pyridyl nitronylnitroxide)_2X (X=Hydroquinine, Fumaric Acid and Squaric Acid)" Journal of Materials Chemistry. 8. 1157-1164 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Asahi, et al.: "Novel Conducting Charge-Transfer Complexes of 1,4,5,8-Naphthalenetetrone (NTO) and 1,4,9,10-anthracenetetrone (ATO)" Synth.Metals. 70. 1117-1118 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Takeda, et al.: "ESR Study on the Charge Transfer Complexes of N-Salicylideneanilines Containing NHO Hydrogen Bond as a Dynamic Function" Synth.Metals. 70. 1211-1212 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] t.Sekikawa, et al.: "Mid-Gap State of the Quasi-One-Dimensional Mott-Hubbard System : Charge Transfer Complex Composed of 1,6-Pyrenediamine and Tetracyanoquinodimethane (DAP-TCNQ)" Synth.Metals. 70. 1213-1214 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Goto, et al.: "High-Resistance Phase and Low-Resistance Phase in 1,6-Diaminopyrene-p-Chloranil (DAP-CHL)" Synth.Metals. 70. 1237-1238 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] J.Kawamata, et al.: "Sallient Nonlinear Optical Properties of Novel Organic Crystals Comprising pi-Conjugated Ketones" Appl.Phys.Lett.66-5. 3102-3104 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Morimoto, et al.: "Conducting Neutral Radical Crystals of Axially Substituted Phthalocyanine : Crystal Structures, Dimensionality, and Electrical Conductivity" J.Mater.Chem.5-10. 1749-1752 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Goto, et al.: "Crystal Structure and Physical Properties of 1,6-Diaminopyrene p-Chloranil (DAP-CHL) Charge-Transfer Complex. Two Polymorphs and their Unusual Electrical Properties" Bull.Chem.Soc.Jpn.69-1. 85-93 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] J.Kawamata, et al.: "Large Second-Harmonic Generation Coefficients of Bis (benzylidene) cycloalkanones Estimated by the Second-Harmonic Wave Generated with the Evanescent Wave Technique" Chem.Phys.Lett.249. 29-34 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Inabe, et al.: "Two-Dimensional Molecular Arrangement in Phthalocyanine Based Conducting Crystals" Mol.Cryst.Liq.Cryst.278. 151-156 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] J.Kawamata, et al.: "Prominent Second-Order Nonlinear Optical Properties of Novel Ketone Derivatives" Mol.Cryst.Liq.Cryst.278. 117-124 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Inabe, et al.: "Unusual Electrical Properties of 1,6-Diaminopyrene Charge-Transfer Complex Crystals" Mol.Cryst.Liq.Cryst.284. 283-290 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Morimoto, et al.: "Molecular Conductors Based on Axially Substituted Phthalocyanine Neutral Radicals" Mol.Cryst.Liq.Cryst.284. 291-300 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Inabe, et al.: "Dimensionality Control of Phthalocyanine Based Conductors" Mol.Cryst.Liq.Cryst.285. 107-112 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Sekikawa, et al.: "Femtosecond Fluorescence Study on the Substitution Effect on the Proton Transfer in Thermochromic Salicylideneaniline Crystals" J.Phys.Chem.A. 101-4. 644-649 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Sekikawa, et al: "Spin-0 Soliton Formation in Spin-Peierls Systems : Charge-Transfer Complexes DAP-TCNQ and DAP-DMTCNQ" Phys.Rev.B. 55-7. 4182-4190 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Inabe, et al.: "Wide Variety of Dimensionality in Phthalocyanine Based Molecular Conductors" Synth.Metals. 86. 1799-1800 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Akutagawa, et al.: "Crystal Structure and Electrical Conductivity of [NH_4^+][18-crown-6][Ni(dmit)_2]_3" Synth.Metals. 86. 1861-1862 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Fujinawa, et al.: "Unusual Electrical Properties of 1 : 1 Charge-Transfer Complexes Composed of 1,6-Diaminopyrene and Some Tetrahalo-p-Benzoquinone" Synth.Metals. 86. 1965-1866 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] E.Ito, H.et al.: "Soft X-ray Absorption and X-ray Photoelectron Spectroscopic Study of Tautomerism in Intramolecular Hydrogen Bonds of N-Salicylideneaniline Derivatives" J.Am.Chem.Soc.119-27. 6336-6344 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Kobayashi, et al.: "Femtosecond Luminescence Study of Hydrogen-Atom-Transfer Prosess in Thermochromic Crystalline Salicylideneanilines" J.Lumin.72-74. 508-510 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Otsuka, et al.: "Crystal Structures and Magnetic Properties of Acid-Base Molecular Complexes, (p-Pyridyl nitronylnitroxide)_2X (x=Hydroquinine, Fumaric Acid and Squaric Acid)" J.Mater.Chem.8-5. 1157-1164 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 関川太郎: "Spin-0 Soliton Formation in Spin-Peierls Systems:Charge-Transfer Complexes DAP-TCNQ and DAP-DMTCNQ" Physical Review B. 55(7). 4182-4190 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 藤縄 祐: "Unusual Electrical Properties of 1:1 Charge-Transfer Complexes Composed of 1,6-Diaminopyrene and Some Tetrahalo-p-benzoquinone" Synthetic Metals. 86. 1865-1866 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 伊藤英輔: "Soft X-ray Absorption and X-ray Photoelectron Spectroscopic Study of Tautomerism in Intramolecular Hydrogen Bonds of N-Salicylideneaniline Derivatives" Journal of the American Chemical Society. 119(27). 6336-6344 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 小林孝嘉: "Femtosecond Luminescence Study of Hydrogen-Atom-Transfer Process in Thermochromic Crystalline Salicylideneanilines" Journal of Luminescence. 72-74. 508-510 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 稲辺 保、他: ""Unusual Electrical Properties of 1,6-Diaminopyrene Charge-Transfer Complex Crystal"" Moleclar Crystals and Liquid Crystals. 284. 283-290 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 関川太郎、他: ""Femtosecond Fluorescence Study of the Substitution Effect on the Proton Transfer in Thermochromic Salicylideneaniline Crystals"" The Journal of Physical Chemistry A. 101. 644-649 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] 朝日秀眞、他: "“Novel Conducting Charge-Transfer Complexes of 1,4,5,8-Naphthalenetetrone(NTO)and 1,4,9,10-anthracenetetrone(ATO)"" Synthetic Metals. 70. 1117-1118 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 武田 定、他: "“ESR Study on the Charge Transfer Complexes of N-Salicylideneanilines Containing NHO Hydrogen Bond as a Dynamic Function"" Synthetic Metals. 70. 1211-1212 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 関川太郎、他: "“Mid-Gap State of the Quasi-One-Dimensional Mott-Hubbard System:Charge Transfer Complex Composed of 1,6-Pyrenediamine and Tetracyanoquinodimethane(DAP-TCNQ)"" Synthetic Metals. 70. 1213-1214 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 後藤裕利、他: "“High-Resistance Phase and Low-Resistance Phase in 1,6-Diaminopyrene-p-Chloranil(DAP-CHL)"" Synthetic Metals. 70. 1213-1214 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 後藤裕利、他: "“Crystal Structure and Physical Properties of 1,6-Diaminopyrene p-Chloranil(DAP-CHL)Charge-Transfer Complex.Two Polymorphs and their Unusual Electrical Properties"" Bulletin of the Chemical Society of Japan. 69. 85-93 (1996)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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