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Development of a high resolution solid-steate NMR spectrometer and investigation dynamical behavior of organic molecules in the solid state.

Research Project

Project/Area Number 02554016
Research Category

Grant-in-Aid for Developmental 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)
TUKADA Hideyuki  Yokohama City Univ., Associate, 総合理学研究所, 助教授 (40171970)
SATO Naoki  Kyoto Univ., Professor, 化学研究所, 教授 (10170771)
YAMAGISHI Akihiko  Univ.of Hokkaido,Dept.of Science, Professor, 理学部, 教授 (70001865)
KOBAYASHI Keiji  Univ.of Tokyo,Dept.of Arts and Sciences,Professor, 教養学部, 教授 (50012456)
藤戸 輝昭  日本電子(株), 分析機器, 研究員
Project Period (FY) 1990 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥19,000,000 (Direct Cost: ¥19,000,000)
Fiscal Year 1992: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1991: ¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 1990: ¥13,600,000 (Direct Cost: ¥13,600,000)
KeywordsSolid-state high resolution NMR / Dynamical behavior of organic molecules in the solid state / Tautomerization in the solid state / Polymerization in the solid state / Polydiacetylene / beta-Hydroxyphenalenone / ヒドロキシフェナレノン / 固体高分解能核磁気共鳴装置 / パルス系列 / 光透過プロ-ブ / 固体 ^1H高分解能測定 / 固相有機分子ダイナミックス / 光透過型プロ-ブ / 心体 ^1H高分解能測定
Research Abstract

The purpose of the project is to produce a new type of a high resolution solid-state NMR spectrometer for investigating dynamical behavior of organic molecules in the solid state.
1. The main instrumental problems to be innovated are as follows.
(1) Optimize pulse frequencies in order to perform CRAMPS experiments (high resolution solid state ^1HNMR) by introducing a four-phase shifter and other hardwares.
(2) Improve a lower limit of variable temperatures for CP/MAS experiments by modifying a cooling system of the probe.
(3) Prepare a photo-transmission probe in order to irradiate a sample during CP/MAS measurements.
The first problem was successfully solved. High resolution ^1H NMR spectra of maleic acid and citric acid were obtained with a resolution of 0.32 ppm. Technical solutions concerning to the latter two points were proposed, although instrumental modifications could not be achieved due to the financial condition.
2. Utilizing the novel spectrometer, CP/MAS measurement were performed on solid samples to elucidate intriguing dynamical behaviors. Typical studies are as follows.
(1) Investigate the solid state tautomerization of b-hydroxyenones which exhibit paraelectric and (anti)ferroelectric behaviors
(2) Prepare new host molecules such as twin-donors or fused thiophenes and elucidate dynamical behaviors of guest molecules in inclusion complexes.
(3) Prepare photolabile diacetylenes carrying a mesogenic group and monitor the photo-induced polymerization by CP/MAS measurements.
In summery, novel physical properties and chemical reactions, which are derived from a dynamical behavior of organic molecules in the solid state, have been elucidated by using the newly developed high resolution solid state NMR spectrometer.

Report

(4 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • 1990 Annual Research Report
  • Research Products

    (31 results)

All Other

All Publications (31 results)

  • [Publications] S.MATSUMIYA et al.: "Effect of Methyl Substitution on Conformation and Molecular Arrangement of BEDT-TTF Derivatives in the Crystalline Environment" Bull.Chem.Soc.Jpan.66. 513-522 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.MAZAKI et al.: "Clathlate Crystals Including the 4-Amino-2,2,6,6-tetramethylpiperidine 1-Oxy1(ATEMPO)Radicals as a Guest Component" J.Chem.Soc.,Chem.Commun.1661-1663 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.SATO: "Monte Carlo Simmulation for the Interactions of Metal Complexes with the Silicate Sheets of a Clay" J.Am.Chem.Soc.114. 9382-9287 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] I.IZUOKA: "An X-ray Crystallographic Analysis of a (BEDT-TTF)_2 C_<60> Charge-transter Complex" J.Chem.Soc.,Chem.Commun.1472-1473 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.OKUNO: "Crystal Structure and Solid State Reactivity of Unsymmetrically Aryl-Substituted Diacetylene" Mol.Cryst.Liq.Cryst.225. 201-205 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] L.Mahe et al.: "How Crystalline Environment can Provide Outstanding Stability and Chemistry for Arylnitrenes" J.Am.Chem.Soc.114. 7904-7906 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 菅原 正: "大橋裕二編〔分子性結晶の反応〕27.配向制御部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., 10P (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Sugawara: "How Can Crystalline Environment Provide Outstanding Stability and Chemistry for Diarylcarbenes or Arylnitrenes.Chap 3,in Chemical Peactions in Moleculan Crystals,Ed.Y.Ohashi,et al." VCH Co,&Kodansha, 11P (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] S. Matsumiya et al.: "Effect of Methyl Substitution on Conformation and Moleculer Arrangement of BEDT-TTF Derivertives in the Crystalline Environment" Bull. Chem. Soc. Jpn.66. 513-522 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y. Mazaki et al.: "Clathlate Crystals Including the 4-Amino-2,2,6,6-tetramethylpiperidine 1-Oxyl (A TEMPO) Radicals as a Guest Component" J. Chem. Soc. Chem. Commun.1661-1663 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H. Sato et al.: "Monte Carlo Simmulation or the Interactions of Metal Complexes with the Silicate Sheets of a Clay" J. Am. Chem. Soc.114. 9382-9287 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A. Izuoka et al.: "An X-ray Crystallographic Analysis of a (BEDT-TTF)_2C_<60> Charge-transfer Complex" J. Chem. Soc. Chem. Commun.1472-1473 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T. Okuno et al.: "Crystal Structure and Solid State Reactivity of Unsymmetrically Aryl-Substituted Diacetylene" Mol. Cryst. Liq. Cryst.225. 201-205 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] L. Mahe et al.: "How Crystalline Environment Can Provide Outstanding Stability and Chemistry for Arylnitrenes" J. Am. Chem. Soc.114. 7904-7906 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Ohashi et al.: "How can Crystalline Environment Provide Outstanding Stability and Chemistry for Diarylcarbenes or Arylnitrenes" "Chemical Reactions in Molecular Crystals" VCH Co. & Kodansha, Ed.Chap.3. 169-177 (1993)

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

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] S. Martsumita er al.: "Effect of Methyl Substitution on Conformation and Molecular Arrangenent of BEDT-TTF Derivatives in the Crystalline Environment" Bull. Chem.Soc. Jpn.66. 513-522 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Y. Mazakiet al.: "Clethlate Crystals Including the 4- Amino-2,2,6,6-tetramethylpiperidine 1-Oxyl(ATEMPO)Radicals as a Guest Component" J. Chem.Soc., Chem Commun.1661-1663 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H. Sato: "Monte Carlo Simmulation for the Interactions of Metal Complexes with the Silicate Sheets of a Clay" J. Am. Chem. Soc.114. 9382-9287 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] A. Izuoka: "An X-ray Crystalographic Analysis of a (BEDT-TTF)_2 C_<60>tjCharge-transfer Complex" J. Chem. Soc. Commun.1472-1473 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] T. Okumo: "Crystal Structure and Solid State Reactivity of Unsymmitrically Aryl-Substituted Diacetylene" Mol.Cryst. Liq. Cryst.225. 201-205 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] L. Mahe et al.: "How Crystalline Environment Can Provide Outstanding Stability and Chemistry for Arylnitrenes" J. Am. Chem. Soc.114. 7904-7906 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] T.mochida: "Crystal Structure of 2-Carboxy-3-hyclroxydiben30tropne;Tautomeric System with an Extremely Short Intramolecular 0…0 Distance" Bull.Chem.Soc.Jpn.

    • Related Report
      1991 Annual Research Report
  • [Publications] T.mochida: "Reconetraction of Hydrogen-Bonded Crystals of 3-Hydroxydiben30tropone Fomed by Solid State Decarboxylation of 2-Carboxy Derivative" Chem.Lett.

    • Related Report
      1991 Annual Research Report
  • [Publications] S.matsumiya: "Conformational Analyais of methylated Dihyarodithiim in ltu BEDT-TTF Skeleton in Crystals" Bull.Chem.Soc.Jpn.,to be Sulmitted.

    • Related Report
      1991 Annual Research Report
  • [Publications] N.Sato: "Linearly Condeused Polythiophenes:Characteristic Mcleculon Aggretion of Tehathienoacene Crystals Disclovd by Ulhaviolat Photoelechon Spechoscopy" J.Chem.Soc.,Perkin 2.

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Magaki: "Crystal and Moleculan Structires of Tetrathienoaceneas a Hydrogu Poor Heterocycle" J.Chem.Soc.,Perkin 2.

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Magaki: "Dynamic Behavicr of the Guest Molecules in the Host-Guest Inclusion Crystals" Chem.Lett.,.

    • Related Report
      1991 Annual Research Report
  • [Publications] 菅原: "Deilectric Properties Locyaling with ProtonーTransfer in 2ーCarboxyー3ーhycrsoxy phenalenone Crystals." J.Am.Chen.Soc.,.

    • Related Report
      1990 Annual Research Report
  • [Publications] 持田: "Structure of 3ーHydroxy phenalenone" Acta Cryst.(C).

    • Related Report
      1990 Annual Research Report
  • [Publications] 泉岡: "Polymerization of LiquidーCrystalline Diacerylenes;Effect of an External Eーloctric Field on the Initcal Rate of Polymerization" Chem.Lett.,.

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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