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1992 Fiscal Year Final Research Report Summary

Development of novel physical properties derived from proton-dynamics in hydrogen-bonded molecular crystals

Research Project

Project/Area Number 02453006
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 物理化学一般
Research InstitutionUniversity of Tokyo

Principal Investigator

SUGAWARA Tadashi  Univ. of Tokyo, Dept. of Arts and Sciences, Professor, 教養学部, 教授 (50124219)

Co-Investigator(Kenkyū-buntansha) IZUOKA Akira  Univ. of Tokyo, Dept. of Arts and Sciences, Research Associate, 教養学部, 助手 (90193367)
SATO Naoki  Kyoto Univ., Institute of Chemical Research, Professor, 化学研究所, 教授 (10170771)
Project Period (FY) 1990 – 1992
KeywordsProton dynamics / Dielectric property / Tautomerization / Phase transition / X-ray crystallographic analysis / Solid state high resolution NMR / Dielectric constant measurement
Research Abstract

This project aims at developing novel physical properties derived from proton dynamics in hydrogen bonded molecular crystals. There are two main topics to be investigated.
1. Elucidation of mechanism of dielectric property derived from tautomerization of beta-hydroxyenones.
Hydrogen bond patterns of 3-hydroxyenones, such as 3- or 9-hydroxy phenalenones were determined by X-ray crystallographic analysis and the possibility of tautomerization of these compounds in the crystalline state were investigated by high resolution solid state ^<13>C NMR (CP/MAS) measurements.
(1) The SHG active crystal of 3-hydroxyphenalenone was obtained. Hydroxyenone forms a one-dimensional hydrogen-bonded array with short O-O distances (2.58A^^゚).
(2) Paraelectric behavior of 2-carboxy-3-hydroxyphenalenone was discovered by dielectric constant measurements. The crystal exhibits antiferroelectric transition at 40K. The switching rate of dipole moment is faster than 10GHz.
(3) The disordered crystal structure of 9-hydroxyphenalenone (Phase II 255-280K) was found to be derived from a dynamic origin based on CP/MAS and dielectric measurements. The molecule undergoes not only a rapid tautomerization but also a 120゚ jumping motion in crystals and exhibits a paramagnetic behavior.
2. Static and dynamic modulation of hydrogen bonds upon the transport property of molecular conductors.
Ni(dmit)_2 complexes involving various counter ion systems connected by hydrogen bonds were prepared. Among them, temperature dependence of conductivity of the Ni(dmit)_2 complex carrying H_3O^+-H_2O-CH_3CN as a counter ion system exhibits a hystereses in the temperature range between 230 and 300K. The anomaly may be explained in terms of the dynamical disturbance caused by supercooled water molecules and oxonium ions which melt in this temperature range. The phenomenon may lead to a novel methodology of controlling physical properties based on dynamic processes which take place in the solid state.

  • Research Products

    (14 results)

All Other

All Publications (14 results)

  • [Publications] T.Mochida et al.: "Structure of 3-Hydroxyphenalenone" Acta Cryst.C48. 680-683 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Sugawara et al.: "Organic Oaraelectrics Resulting from Tautomerization Coupled with Proton-transfer" Solid State Commun.83. 665-668 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Sugawara et al.: "Physical Properties derived from proton Dynamic in Hydrogen-Bonded Organic Molecular Crystals" Mol.Cryst.Liq.Cryst.218. 291-296 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Miyazaki et al.: "Crystal Structure of(ImH)(Mi(dmit))22 with intercolumnar Interaction through an imidazolium counterion" Bull.Chem.Soc.Jpn.65. 2528-2530 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Miyazaki et al.: "Structural and Electrostatic Modulation by Hydrogen Bonds upon the Conduction Column of Ni(dmit)2 complex" Mol.Cryst.Liq.Cryst.216. 217-222 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 菅原 正: "大橋裕二編〔分子性結晶の反応〕27.配向制御位を有するジアセチレンの固相液晶相重合反応の解析" Realize.Inc., 10 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Sugawara: "How Can Crystalline Environment Provide Outstanding Stability and Chemistry for Diarylcarbenes or Arylnitrenes,Chap.3,in Chemical Reactions in Molecular Crystals,Ed.Y.Omashi,et al.," VCH Co,&Kodansha, 11 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Mochida et al.: "Structure of 3-Hydroxyphenalenone" Acta Cryst.C48. 680-683 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Sugawara et al.: "Organic Paraelectrics Resulting from Tautomerization Coupled with Proton-transfer" Solid. State Commun.83. 665-668 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Sugawara et al.: "Physical Properties Derived from Proton Dynamics in Hydrogen-Bonded Organic Moleculer Crystals" Mol. Cryst. Liq. Cryst.218. 291-296 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Miyazaki et al.: "Crystal Structure of (ImH)(Ni(dmit)_2)_2 with intercolumnar Interaction through an Imidazolium Counter Ion" Bull. Chem. Soc. Jpn.65. 2528-2530 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Miyazaki et al.: "Structural and Electrostatic Modulation by Hydrogen Bonds upon the Conduction Column of Ni(dmit)_2 Complex" Mol. Cryst. Liq. Cryst.216. 217-222 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Sugawara: "Mchaism of Solid State and Liquid Crystal State Polymerization of Diacetylenes with Orientation- Controling Group (in Japanese)" "Reactions in Molecular Crystals" Realize. Inc., Ed. by Y.Ohashi. 265-274 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Sugawara: "How can Crystalline Environment Provide Outstanding Stability and Chemistry for Diarylcarbenes or Arylnitrenes" "Chemical Reactions in Molecular Crystals", VCH Co. & Kodansha Ed. by Y.Ohashi et al., Chap.3. 169-177 (1993)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1994-03-24  

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