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Kinetic Studies on the Reaction of Pyridinyl Radicals byMeans of Time-Resolved Magnetic Resonance Spectroscopy

Research Project

Project/Area Number 60430001
Research Category

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

Allocation TypeSingle-year Grants
Research Field 物理化学一般
Research InstitutionTOHOKU UNIVERSITY

Principal Investigator

IKEGAMI Yusaku  Chemical Research Institute of Non-Aqueous Solutions, Tohoku University, Professor, 排水溶液科学研究所, 教授 (60006294)

Co-Investigator(Kenkyū-buntansha) TERO Shozo  Chemical Research Institute of Non-Aqueous Solutions, Tohoku Universiry, Associa, 非水溶液科学研究所, 助教授 (80111318)
AKIYAMA Kimio  Chemical Research Institute of Non-Aqueous Solutions, Tohoku University, Assista, 排水溶液科学研究所, 助手 (10167851)
ONODERA Shinji  Chemical Research Institute of Non-Aqueous Solutions, Tohoku University, Associa, 排水溶液科学研究所, 助教授 (30006316)
Project Period (FY) 1985 – 1987
Project Status Completed (Fiscal Year 1987)
Budget Amount *help
¥17,000,000 (Direct Cost: ¥17,000,000)
Fiscal Year 1987: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1986: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 1985: ¥13,000,000 (Direct Cost: ¥13,000,000)
Keywordstime-resolved ESR / ESR / CIDEP / pyridinyl radical / diradical / kinetic ESR / spin polarization / エネルギーの移動 / 光化学反応 / フォトエノール / ラジカル二量化反応電子スピン共鳴 / CIDNP
Research Abstract

Kinetic studies for the convertible monomer-dimer systems of pyridinyl radicals have been carried out.
1. ESR and NMR spectrometer systems were fully equipped for the detection of chemically induced electron and nuclear spin polarization (CIDEP and CIDNP) phenomena.
2. Kinetic parameters for the dimerization of various pyridinyl radicals were determined by the use of a kinetic ESR systems. The dimerization mechanisms with and without intervension of intermediate were discussed.
3. The CIDEP studies on the photochemical cleavage of pyridinyl radical dimers elcuidated that the radicals are generally produced through the singlet radical pair precursor, since an A(absorption)/E(emission) pattern was exhibited in the transient ESR spectra.
4. A spin polarization conservation during excitation energy transfer in solution was firstly observed in the CIDEP measurements for the photodissociation of the 1-methyl-4-alkylpyridinyl radical dimers in the presence of triplet sensitizers. This suggests a possibility of the dimer photodissociation from the triplet state.
5. The 1,1'-ethylenebis- and 1,1'-trimethylenebis-(pyridinyl) diradicals exist as the diamagnetic cyclomers of dl and meso forms at room temperature. Both forms photodissociate to generate the diradical, which can be detected at 77 K.
6. Application of time-resolved ESR measurement to some organic photoreactions led to exciting results in the detection of intermediates.

Report

(3 results)
  • 1987 Final Research Report Summary
  • 1986 Annual Research Report
  • 1985 Annual Research Report
  • Research Products

    (31 results)

All Other

All Publications (31 results)

  • [Publications] Kimio Akiyama: Bulletin of the Chemical Society of Japan. 58. 3535-3538 (1985)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Yusaku Ikegami: Reviews of Chemical Intermediates. 7. 91-109 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Yusaku Ikegami: Journal of the American Chemical Society. 109. 2876-2880 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Takashi Muramatsu: Chemicatry Letters. 2139-2142 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Takashi Muramatsu: Chemistry Letters. 1683-1686 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Kimio Akiyama: Chemistry Letters. 255-256 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Kimio Akiyama: Bulletin of the Chemical Society of Japan. 59. 3269-3270 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Kimio Akiyama: Journal of the American Chemical Society. 109. 2538-2539 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Hirami Shimoishi: Chemistry Letters. 251-254 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Shozo Tero-Kubota: Journal of Chemical Society, Chemical Communication.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Kimio Akiyama: "Photolytic Generation and the Subsequent Dimerization of 4-Alkyl-1-methylpyridinyl Radicals in Solution as Studied by Steady-state and Kinetic ESR Spectroscopy" Bull. Chem. Soc. Jpn.58. 3535-3539 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Yusaku Ikegami: "Kinetic ESR and CIDEP Studies on the Monomer-Dimer Equilibrium Systems of Pyridinyl Radicals" Rev. Chem. Intermed.7. 91-109 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Yusaku Ikegami: "The 1,1'-Ethylenebis[4-(methoxycarbonyl)pyridinyl] Diradical and Its Photosensitive Cyclomers" J. Am. Chem. Soc.109. 2876-2880 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Takashi Muramatsu: "Photochemical Generation of 1,1'-Ethylenebis(pyridinyl) Diradical from ItsCyclomer" Chem. Lett.2139-2142 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Takashi Muramatsu: "The 1,1'-Trimethylenebis(pyridinyl) Diradical and Its Photosensitive Cyclomers" Chem. Lett.1683-1686 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Kimio Akiyama: "The Polarized ESR Spectrum of 1-Methyl-3-methoxycarbonylpyridinyl Radical" Chem. Lett.255-256 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Yusaku Ikegami: "The Photosensitive Cyclomer Formation of 1,1'-Ethylenebis(pyridinyl) Diradical and Its Derivatives" J. Am. Chem. Soc.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Yusaku Ikegami: "The 1,1'-Trimethylenebis(pyridinyl) Diradicals and the Cyclomer Formation" J. Am. Chem. Soc.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Kimio Akiyama: "A Time-Resolved ESR Study on the Photochemical Reduction of Nirobenzene Derivatives in Alcoholic Solution" Bull. Chem. Soc. Jpn.59. 3269-3270 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Kimio Akiyama: "Polarized ESR Spectra of the Triplet Enols Generated from o-Methylacetophenone and Related Compounds" J. Am. Chem. Soc.,. 109. 2538-2539 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Hiramai Shimoishi: "A CIDEP Study on the Photoreaction Mechanism of o-Quinones" Chem. Lett.251-254 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Hirami Shimoishi: "Time-Resolved ESR Studies on the Photoreaction Mechanism of o-Quinones"

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Shozo Tero-Kubota: "Time-Resolved ESR Study on the Triplet Ketoamines Generated from Intramolecular Proton Transfer of Free Schiff Bases" J. Chem. Soc., Chem. Commun.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Kimio Akiyama: Bulletin of the Chemical Society of Japan. 58. 3535-3539 (1985)

    • Related Report
      1986 Annual Research Report
  • [Publications] Yusaku Ikegami: Reviews of Chemical Intermediates. 7. 91-109 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] Takashi Muramatsu: Chemistry Letters. 2139-2142 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] Yusaku Ikegami: Journal of the American Chemical Society. 109. (1987)

    • Related Report
      1986 Annual Research Report
  • [Publications] Kimio Akiyama: Journal of the American Chemical Society. 109. (1987)

    • Related Report
      1986 Annual Research Report
  • [Publications] Yusaku Ikegami: Chemistry Letters.

    • Related Report
      1986 Annual Research Report
  • [Publications] Bull.Chem.Soc.Japan. 58-12. (1985)

    • Related Report
      1985 Annual Research Report
  • [Publications] Rev.Chem.Intermed.7-1. (1986)

    • Related Report
      1985 Annual Research Report

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Published: 1987-03-31   Modified: 2016-04-21  

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