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Development of the CIDNP Detected ESR Method and the Research on the Short-Lived Paramagnetic Species.

Research Project

Project/Area Number 62430001
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

AZUMI Tohru  Tohoku University, Faculty of Science, Professor, 理学部, 教授 (90013490)

Co-Investigator(Kenkyū-buntansha) TERAZIMA Masahide  Tohoku University, Faculty of Science, Assistant, 理学部, 助手 (00188674)
Project Period (FY) 1987 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥24,900,000 (Direct Cost: ¥24,900,000)
Fiscal Year 1989: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1988: ¥9,000,000 (Direct Cost: ¥9,000,000)
Fiscal Year 1987: ¥13,400,000 (Direct Cost: ¥13,400,000)
KeywordsCIDNP / CIDEP / ESR / EPR / Radical pair / Enhancement factor / L-band ESR / Dibenzilketone / 反応中間体 / stimulated nuclear polarization / dynamic nuclear polarization / ベンゾキノン / 磁場効果 / 化学反応 / 光化学反応
Research Abstract

The most direct purpose of this research project is to develop the CIDNP detected ESR method as an aid to detect the radical pair. In addition, however, we have other, similarly important purposes: (a) To develop the method to quantitatively measure the CIDNP intensity. (b) To develop the method of analysis from both CIDNP and CIDEP. For all the three points described above, we were able to obtain significant results. They are summarized in the following.
1. The method of determining the CIDNP enhancement factor has been established. 2. The mechanism of the photochemical cleavage of benzoyl peroxide is analyzed, and continuous diffusion process is examined. 3. The method to determine the precursor of the photochemical reaction from the CIDNP method is re-examined in terms of the enhancement factor. 4. Magnetic field effect of CIDNP is examined. 5. A new mechanism is proposed in the spin correlated CIDEP mechanism. 6. Exchange interaction is analyzed from both CIDEP and CIDNP. 7. CIDNP detected ESR method has been successfully developed. 8. Low field CIDEP method is established by using L-band ESR spectrometer.

Report

(4 results)
  • 1989 Annual Research Report   Final Research Report Summary
  • 1988 Annual Research Report
  • 1987 Annual Research Report
  • Research Products

    (68 results)

All Other

All Publications (68 results)

  • [Publications] M.Terazima: "Measurement of the Triplet Lifetime and the Quantum Yield of Triplet Formation of Phthalazine by the Time-Resolved Thermal Lens Method." Chem.Phys.Lett.141. 237-240 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.A.Al-Hassan: "Red Edge Effect(REE)Phenomena of Flexible Solute Molecules as a Probe for Polymer Rigidity and/or Free Volume." Chem.Phys.Lett.145. 49-54 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Terazima: "The Quantum Yield of Triplet Formation and Triplet Lifetime in the Solid Phase by a Time-Resolved Thermal Lens Method.Application to Pyridazine." Chem.Phys.Lett.145. 286-288 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Ikeyama: "Properties of the Triplet Spin Sublevels of trans-Stilbene." J.Phys.Chem.92. 1383-1384 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Azumi: "Electronic Structure of the Lower Triplet Sublevels of Hexanuclear Molybdenum(II)Chloride Cluster." J.Phys.Chem.92. 1715-1721 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.A.Al-Hassan: "The Role of Free Volume in the Twisted Intramolecular Charge Transfer(TICT)Emission of Dimethylaminobenzo-nitrile and Related Compounds in Rigid Polymer Matrices." Chem.Phys.Lett.146. 121-124 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Azumi: "Delayed Fluorescence and Triplet-Triplet Annihilation in a Diplatinate(II)Pyrophosphite Complex." SPIE-Int.Soc.Opt.Eng.910. 176-180 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.A.Al-Hassan: "The Red Edge Effect as a Tool for Investigating the Origin of the anomalous Fluorescence Band of 9,9'-Bianthryl in Rigid Polar Polymer Matrices." Chem.Phys.Lett.150. 344-348 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Terazima: "The Quantum Yield of Triplet Formation and Triplet Lifetime of Pyridine in the Liquid Phase by the Two-Photon-Excited Time-Resolved Thermal Lens Method." Chem.Phys.Lett.153. 27-32 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Yamaguchi: "Change in the Color of Luminescence Accompanied by Dehydration of the Solid K_4[Pt_2(P_2O_5H_2)_4]・2H_2O." J.Cord.Chem.18. 223-226 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Ikeyama: "Vibrational Analysis of Sublevel Phosphorescence Spectra of Potassium Tetrakis(μ-diphosphonato)diplatinate(II).Mechanism of Radiative Transition for the Electronically Forbidden A _<1u> Spectrum." J.Phys.Chem.92. 6899-6901 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] O.Ito: "The Photoluminescence of Poly(methylphenylsilylene).The Origin of the Long-Wavelength Broad Band." Macromolecules. 22. 1718-1722 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Terazima: "Limitation of Absorbance Measurements Using the Thermal Lens Method." Anal.Chem.61. 883-888 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Terazima: "Direct Measuriment of the Enthalpy Difference Between Enol and Keto Form by the Time-Resolved Thermal Lens Method: 7-Hydroxyqunoline." J.Am.Chem.Soc.111. 3824-3826 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Terazima: "Observation of Transient Absorption by Using the Thermal Lens Method." Appl.Phys.Lett.54. 2398-2399 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Terazima: "Picosecond Laser Spectroscopy of Poly(methylphenyl silylene).Confirmation of Previous Assignment of the Broad Band." Chem.Phys.Lett.160. 319-323 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Terazima: "Limitation of Absorbance Measurement by Using Photoacounstic Method." Bull.Chem.Soc.Jpn.62. 2862-2866 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Al-Hassan: "Fluorescence Decay Characteristics of 4-Dimetylaminobenzonitrile in Different Polymer Matrices:A Time Resolved Study in the Nanosecond Range." Chem.Phys.Lett.163. 129-134 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Terazima: "CIDEP Studies on the Intramolecular Hydrogen Abstraction Reaction of Polymethylene Linked System.Population Relaxation Between the S-T_0 Mixed States." Chem.Phys.Lett.164. 562-566 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Terazima: "CIDEP and CIDNP Studies on Hydrogen Abstraction of 9,10-Anthraquinone from Xanthene." J.Chem.Soc.Faraday Trans.86. 253-256 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] N.Okabe: "Spin-Sublevel Properties of the π,π^* Triplet State of 2,2'-Bipyridine.Is the out-of-plane Component Most Emissive?" Chem.Phys.Lett.165. 24-27 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] O.Ito: "Phosphorescence and Optical Detection of Magnetic Resonance Studies of Poly(methylpropylsilylene)." J.Am.Chem.Soc.112. 444-445 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] S.Takahashi: "Temperature Dependence on the Enhancement Factor of CIDNP Created by the Photolysis of Benzoylperoxide." Chem.Phys.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Terazima: "A Time-resolved Photoacoustic Method with Pulsed Laser Excitation in the Condensed Phase: The Relation Between Signal Intensity and Decay Constant." Bull.Chem.Soc.Jpn.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Terazima: "Measurement of the Quantum Yield of the Triplet Formation of Transient Species by Using the Transient Time Resolved Thermal Lens Method." Photoacoustic and Phtothermal Phenomena(Springer-Verlag)(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] S.Itoh: "The Exchange Interaction in the Radical Pair in 2-Propanol Solution as Studied by the CIDNP Multiplet Pattern." submitted.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.B.Sakata: "Measurement of the Enhancement Factor of CIDNP in the Photolysis of Dibenzyl Ketone;Determination of the Spin Multiplicity of the Precursor." submitted.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Maeda: "CIDNP and CIDEP Studies on the Intramolecular Hydrogen Abstruction Reaction of the Polymethylene Linked Xanthone and Xanthene;Determination of the Exchange Integral of the Intermediate Biradicals." submitted.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Terazima and T. Azumi: "Measurement of the Triplet Lifetime and the Quantum Yield of Triplet Formation of Phthalazine by the Time-Resolved Thermal Lens Method." Chem. Phys. Lett.141. 237-240 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. A. Al-Hassan and T. Azumi: "Red Edge Effect (REE) Phenomena of Flexible Solute Molecules as a Probe for Polymer Rigidity and/or Free Volume." Chem. Phys. Lett. 145, 49-54 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Terazima and T. Azumi: "The Quantum Yield of Triplet Formation and Triplet Lifetime in the Solid Phase by a Time-Resolved Thermal Lens Method. Application to Pyridazine." Chem. Phys. Lett. 145, 286-288 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Ikeyama and T. Azumi: "Properties of the Triplet Spin Sublevels of trans-Stilbene." J. Phys. Chem. 92, 1383-1384 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Azumi and Y. Saito: "Electronic Structure of the Lower Triplet Sublevels of Hexanuclear Molybdenum(II) Chloride Cluster." J. Phys. Chem. 92, 1715-1721 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. A. Al-Hassan and T. Azumi: "The Role of Free Volume in the Twisted Intramolecular Charge Transfer (TICT) Emission of Dimethylaminobenzonitrile and Related Compounds in Rigid Polymer Matrices." Chem. Phys. Lett. 146, 121-124 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Azumi: "Delayed Fluorescence and Triplet-Triplet Annihilation in a Diplatinate(II) Pyrophosphite Complex." SPIE-Int. Soc. Opt. Eng. 910, 176-180 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. A. Al-Hassan and T. Azumi: "The Red Edge Effect as a Tool for Investigating the Origin of the Anomalous Fluorescence Band of 9,9'-Bianthryl in Rigid Polar Polymer Matrices." Chem. Phys. Lett. 150, 344-348 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Terazima and T. Azumi: "The Quantum Yield of Triplet Formation and Triplet Lifetime of Pyridine in the Liquid Phase by the Two-Photon-Excited Time-Resolved Thermal Lens Method." Chem. Phys. Lett. 153, 27-32 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Yamaguchi, Y. Sasaki, T. Ikeyama, T. Azumi, and T. Ito: "Change in the Color of Luminescence Accompanied by Dehydration of the Solid K_4[Pt_2(P_2O_5H_2)_4]・2H_2O." J. Cord. Chem. 18, 223-226 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Ikeyama, S. Yamamoto, and T. Azumi: "Vibrational Analysis of Sublevel Phosphorescence Spectra of Potassium Tetrakis(mu-diphosphonato)-diplatinate(II). Mechanism of Radiative Transition for the Electronically Forbidden A_<1u> Spectrum." J. Phys. Chem. 92, 6899-6901 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] O. Ito, M. Terazima, T. Azumi, N. Matsumoto, K. Takeda, and M. Fujino: "The Photoluminescence of Poly(methylphenylsilylene). The Origin of the Long-Wavelength Broad Band." Macromolecules 22, 1718-1722 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Terazima, M. Horiguchi, and T. Azumi: "Limitation of Absorbance Measurements Using the Thermal Lens Method." Anal. Chem. 61, 883-888 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Terazima and T. Azumi: "Direct Measurement of the Enthalpy Differences Between Enol and Keto Form by the Time-Resolved Thermal Lens Method: 7-Hydroxyqunoline." J. Am. Chem. Soc. 111, 3824-3826 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Terazima and T. Azumi: "Observation of Transient Absorption by Using the Thermal Lens Method." Appl. Phys. Lett. 54, 2398-2399 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Terazima, O. Ito, and T. Azumi: "Picosecond Laser Spectroscopy of Poly(methylphenylsilylene). Confirmation of Previous Assignment of the Broad Band." Chem. Phys. Lett. 160, 319-323 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Terazima and T. Azumi: "Limitation of Absorbance Measurement by Using Photoacoustic Method." Bull. Chem. Soc. Jpn. 62, 2862-2866 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Al-Hassan and T. Azumi: "Fluorescence Decay Characteristics of 4-Dimethylaminobenzonitrile in Different Polymer Matrices: A Time Resolved Study in the Nanosecond Range." Chem. Phys. Lett. 163, 129-134 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Terazima, K. Maeda, T. Azumi, Y. Tanimoto, N. Okada, and M. Itoh: "CIDEP Studies on the Intramolecular Hydrogen Abstraction Reaction of Polymethylene Linked System. Population Relaxation Between the S-T_0 Mixed State." Chem. Phys. Lett. 164, 562-566 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Terazima, K. Maeda, M. Sugawara, S. Takahashi, and T. Azumi: "CIDEP and CIDNP Studies on Hydrogen Abstraction of 9,10-Anthraquinone from Xanthene." J. Chem. Soc. Faraday Trans. 86, 253-256 (1990).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] N. Okabe, T. Ikeyama, and T. Azumi: "Spin-Sublevel Properties of the pi,pi^* Triplet State of 2,2'-Bipyridine. Is the out-of-plane Component Most Emissive?" Chem. Phys. Lett. 165, 24-27 (1990).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] O. Ito, M. Terazima, and T. Azumi: "Phosphorescence and Optical Detection of Magnetic Resonance Studies of Poly(methylpropylsilylene)." J. Am. Chem. Soc. 112, 444-445 (1990).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] S. Takahashi, M. Terazima, and T. Azumi: "Temperature Dependence on the Enhancement Factor of CIDNP Created by the Photolysis of Benzoylperoxide." Chem. Phys.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Terazima and T. Azumi: "A Time-resolved Photoacoustic Method with Pulsed Laser Excitation in the Condensed Phase: The Relation Between Signal Intensity and Decay Constant." Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Terazima and T. Azumi: "Measurement of the Quantum Yield of the Triplet Formation of Transient Species by using the Transient Time Resolved Thermal Lens Method." Photoacoustic and Photothermal Phenomena (Springer-Verlag).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] S. Itoh, M. Terazima, and T. Azumi: "The Exchange Interaction in the Radical Pair in 2-Propanol Solution as Studied by the CIDNP Multiplet Pattern."

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. B. Sakata, S. Takahashi, M. Terazima, and T. Azumi: "Measurement of the Enhancement Factor of CIDNP in the Photolysis of Dibenzyl Ketone; Determination of the Spin Multiplicity of the Precursor."

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Maeda, M. Terazima, T. Azumi, Y. Tanimoto, N. Okada, and M. Itoh: "CIDNP and CIDEP Studies on the Intramolecular Hydroger Abstruction Reaction of the Polymethylene Linked Xanthone and Xanthene; Determination of the Exchange Integral of the Intermediate Biradicals."

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Terazima: "CIDEP and CIDNP Studies on Hydrogen Abstraction of 9,10ーAnthraquinone from Xanthene." J.Chem.Soc.Faraday Trans.86. 253-256 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] N.Okabe: "SpinーSublevel Properties of the pi,pi^*Triplet State of 2,2′ーBipyridine.Is the outーofーplane Component Most Emissive?" Chem.Phys.Lett.165. 24-27 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] S,Takahashi: "Temperature Dependence on the Enhancement Factor of CIDNP Created by the Photolysis of Benzoylperoxide." Chem.Phys.

    • Related Report
      1989 Annual Research Report
  • [Publications] S,Itoh: "The Exchange Interaction in the Radical Pair in 2ーPropanol Solution as Studied by the CICNP Multiplet Pattern." Chem.Phys.Lett.

    • Related Report
      1989 Annual Research Report
  • [Publications] T.B.Sakata: "Measurement of the Enhancement Factor of CIDNP in the Photolysis of Dibenzyl Ketone;Determination of the Spin Multiplicity of the Precursor." Chem.Phys.

    • Related Report
      1989 Annual Research Report
  • [Publications] K.Maeda: "CICNP and CIDEP Studies on the Intramolecular Hydrogen Abstruction Reaction of the Polymethylene Linked Xanthone and Xanthene;Determination of the Exchange Integral of the Intermediate Biradicals" J.Chem.Phys.

    • Related Report
      1989 Annual Research Report
  • [Publications] M.Terazima: The Journal of Physical Chemistry.

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Maeda: The Journal of Physical Chemistry.

    • Related Report
      1988 Annual Research Report
  • [Publications] S.Takahashi: The Journal of Physical Chemistry.

    • Related Report
      1988 Annual Research Report
  • [Publications] M. Terazima; S. Takahashi; K. Maeda; M. Sugawara; T. Azumi: Journal of Physical Chemistry.

    • Related Report
      1987 Annual Research Report
  • [Publications] S. Takahashi; M. Terazima; T. Azumi: Journal of Physical Chemistry.

    • Related Report
      1987 Annual Research Report
  • [Publications] M. Terazima; S. Takahashi; K. Maeda; M. Sugawara; T. Azumi: Journal of Physical Chemistry.

    • Related Report
      1987 Annual Research Report

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Published: 1987-04-01   Modified: 2016-04-21  

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