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Novel local D-A interactions and physical properties in organic mixed crystals

Research Project

Project/Area Number 13640579
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 InstitutionKobe University

Principal Investigator

HASHIMOTO Masao  Kobe University, Dept. Chemistry, Assoc. Professor, 理学部, 助教授 (90030775)

Co-Investigator(Kenkyū-buntansha) YAMAMURA Kimiaki  Kobe University, Dept. Chemistry, Professor, 理学部, 教授 (60031358)
Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2002: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2001: ¥2,800,000 (Direct Cost: ¥2,800,000)
Keywordsmixed crystal / solid solution / crystal structure / phase transition / D-A interaction / hydrogen bond / supramolecular / clathrate / 昆晶 / 熱解析 / トリプチセン / ベンジルアルコール / 尿素 / X線構造 / 熱分析 / トリプチセンキノ / アズレン
Research Abstract

Local D-A interactions and some physical-chemical properties in mixed crystals of organic compounds were investigated. The materials studies were derivatives of triptycene, azulene, 4-substitutedbenzyl alcohols and alkyl urea.
A new method of preparation of triptycenequinone (TPQ)/triptycenehydroquinone (TPHQ) mixed crystal was found. Crystal structures were determined for bis-(Bromomethyl)triptycene (bis-BrMe-TPQ) and its several clathrates. A mixed crystal of the compound with bis-(bromomethyl)triptycenehydroquinone (bis-BrMe-TPHQ) exhibited local D-A interaction.
Four membered ring type H-bond systems and phase transition were found for bis-(hydroxy)triptycenes. From the knowledge of the crystal structure, an interesting dielectric property is expected for its mixed crystal with hydroxytriptycene.
The crystal structure of 6,7-dimethoxytriptycene suggests that it cannot form a TPQ/TPHQ type mixed crystal. X-ray structure of 5,12-dihydro-o-5,12-benzenonaphthacne-1,4-dione revealed the presence of its clathrate with benzene and this result indicates that a local D-A interaction in a mixed crystal would be possible by changing the guest from benzene to other methyl-benzenes.
For mixed crystals of p-substitutedbenzyl alcohols, composition dependence of the characteristics of the phase transitions, as well as an isotope effect on the transition behavior, were investigated in detail. These results contributed to elucidate the transition mechanism of the compounds.
Among a series of alkyl-ures, octyl-urea exhibited a novel phase transition accompanied by a very large enthalpy change. Mixed crystals of octyl- and heptyl-urea were found to show a transition characteristic that was very dependent on the composition, giving useful information on the transition mechanism.

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] M.Hashimoto, et al.: "Phase transitions, H-bond and crystal dynamics of p-methylbenzyl alcohol"Z.Naturforsch.. 57a. 388-394 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Yamamura, et al.: "Crystal structure of 6,7-dimethoxy-triptycenequinone"Anal.Sci.. 18. 1405-1406 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Hashimoto, et al.: "Tetrameric hydrogen-bonds in 1,4-bis(hydroxymethyl)triptycene"J.Mol.Struct.. 616. 129-134 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Yamamura, et al.: "Crystal structure of dihydrobenzenonaphthalene with benzene (2:1)"Anal.Sci.. 19. 467-468 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Hashimoto, et al.: "Conformational phase transitions in 4-Chioro and 4-bromobenzyl alcohols"Z.Naturforsch.. 58a. 63-67 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Hashimoto, M. Harada, M. Mizuno, M. Hamada, T. Ida, and M. Suhara: "Phase Transitions, Hydrogen Bond and Crystal Dynamics of p-Methylbenzyl Alcohol as Studied by Single Crystal X-ray Diffraction and ^2H NMR"Z. Naturforsch.. 57a. 388-394 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Yamamura, T. Kawashima, and M. Hashimoto: "Crystal structure of 6,7-Dimethoxy-triptycenequinone"Anal. Sci.. 18. 1405-1406 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Hashimoto, F. Tajima, and K. Yamamura: "Tetrameric O-H…O hydrogen-bond systems accompanied by C-H…O hydrogen-bonds in the crystal of 1,4-bis(hydroxymethtyl)triptycene: an X-ray study"J. Mol. Struct.. 616. 129-134 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Yamamura, J. Yamane, and M. Hashimoto: "Crystal structure of clathrate of 5,12-dihydro-5, 12-o-benzenonaphthacene-1,4-dione with benzene (2:1)"Anal. Sci.. 19. 467-468 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Hashimoto, and M. Harada: "Coformational Phase Transitions Associated with Reversal of Hydrogen Bond Direction in 4-Chloro- and 4-Bromobenzyl Alcohols. An X-Ray Study"Z. Naturforsch.. 58a. 63-67 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masao Hashimoto: "Tetrameric O-H...O hydrogen-bond systems accompanied by C-H...O hydrogen-bonds in the crystal of 1,4-bis(hydroxymethtyl)triptycene : an X-ray study"J.Mol.Struct.. 616. 129-134 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Masao Hashimoto: "Coformational Phase Transitions Associated with Reversal of Hydrogen Bond Direction in 4-Chloro-and 4-Bromobenzyl Alcohols. An X-Ray Study"Z.Naturforsch.. 58a. 63-67 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Kimiaki Yamamura: "Crystal structure of 6,7-Dimethoxy-triptycenequinone"Anal.Sci.. 18. 1405-1406 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Kimiaki Yamamura: "Crystal Structure of 1,1,1-triphenyl-4-(1O-benz[a]azulenyl)-3,4-butene-2-one"Anal.Sci.. 18. 373-374 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Kimiaki Yamamura: "Crystal Structure of 1,1,1-triphenyl-4-(1O-benz[a]azulenyl)-2-butanone"Anal.Sci.. 18. 499-500 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Kimiaki Yamamura: "Novel and facile synthesis of β-(4-azuleno[1,2-b]thienyl)-and β-(4-azuleno[2,1-b]thienyl)-α,β-unsaturated ketones by intramolecular tropylium ion-mediated furan ring-opening reaction"Tetrahedron. 58. 7653-7661 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Hashimoto, et al.: "Phase Transitions, Hydrogen Bond and Crystal Dynamics of p-Methylbenzyl Alcohol as Studied by Single Crystal X-Ray Diffraction and 1-H NMR"Z. Naturforsch.. 57a(in press). (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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