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Photochemical Reaction of Metal Complexes Studied by Advanced EPR

Research Project

Project/Area Number 07044058
Research Category

Grant-in-Aid for international Scientific Research

Allocation TypeSingle-year Grants
SectionJoint Research
Research InstitutionInstitute of Chemical Reaction Science Tohoku University

Principal Investigator

YAMAUCHI Seigo  Institute of Chemical Reaction Science, Tohoku University, Professor, 反応化学研究所, 教授 (10127152)

Co-Investigator(Kenkyū-buntansha) DINSE Klaus-Peter  Physical Chemistry III,TH Darmstadt, 物理化学科, 教授
MOBIUS Klaus  Department of Physics, Free University of Berlin, 実験物理学研究所, 教授
OHBA Yasunori  Institute of Chemical Reaction Science, Tohoku University, 反応化学研究所, 助教授 (10176985)
AKIYAMA Kimio  Institute of Chemical Reaction Science, Tohoku University, 反応化学研究所, 助教授 (10167851)
DINSE Klaus  ダームスタット工科大学, 物理化学科, 教授
Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 1996: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 1995: ¥2,900,000 (Direct Cost: ¥2,900,000)
KeywordsPulsed EPR / Multi-Dimension / W-band / Time-Resolved EPR / Nutation / Photoinduced electron Transfer / FT-EPR / Metalloporphyrin / Excited Multiplet / 光化学反応 / 電子スピン共鳴 / 多次元 / 光合成 / 金属ポリフィリン / 金属フラーレン
Research Abstract

In this study we developed new EPR machines and studied photophysics and photochemistry of metal complexes with these laboratory-made EPR apparatus. The following results were obtained :
1) The Fourier transform (FT) EPR machine was constructed by modifying our spin echo system for analyzes of photochemical reactions. The experiments of high time-resolution (10ns) and multi-dimensional modes were made possible with this machine.
2) In Mobius' laboratory, the W-band EPR machine was constructed and used both in time-resolved and pulsed modes, which has the higher time-resolution (5ns).
3) The electron spin polarization transfer was verified for the firsr time in the triplet-doublet system, where we used excited triplet metalloporphyrins and nitroxide radicals. By means of this technique we measured the spin-lattice relaxation times of radicals and observed the spectra of non-polarized radicals.
4) The two-dimensional nutation method was applied for the first time in the transient EPR experiment ; mettalloporphyrin-quinone in micellar system. The photochemical intermediate was separated spectroscopically from the radicals and definitely assigned as an ion pair.
5) New microwave-pulse sequences were developed and applied to the study of molecular dynamics of metallofullerenes. Temperature dependence of the signal was examined and analyzed in terms of molecular liblations and spin dynamics.
6) Triplet-radical pair systems were constructed with metalloporphyrins ligated by pyridinyl-nitroxied radicals. Two kinds of EPR signals were separeted by the W-band EPR technique and assigned by the two-dimensional nutation technique as those of the excited quartet and doublet states.
In addition to these scienfically important results, We succeeded in making acontract between our Laboratory and Department of Physics of Berlin Free University and in holding the international Sendai Symposium twice.

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (58 results)

All Other

All Publications (58 results)

  • [Publications] K.Ishii: "Studies on Monomers and Dimers of Y (III) and La (III) Porphyrin Complexes by means of TREPR" J.Phys.Chem.100. 3839-3846 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Yamauchi: "State Mixing in the Excited Triplet and Singlet States of Magnesium Tetraphenylporphines" Inorg.Chem.35. 2910-2914 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] R.Hanaishi: "1D and 2D FT-EPR Studies on the Photo-induced Electron Transfer Reaction" Bull.Chem.Soc.Jpn.69. 1533-1541 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N.Okabe: "Electron Spin Relaxation Studies of LaC_<82> in the Solid State by EPR" Appl.Magn.Reson.10. 251-262 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] R.Hanaishi: "Two Dimensional FT-EPR Spectroscopy for Spin-Correlated Radical Pairs and Solution" Appl.Magn.Reson.10. 55-69 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Ohkoshi: "Photodissociation of Bis (S-benzyl-1,2-diphenyl-1,2-ethylenedithiolato) metal Complexes" Inorg.Chem.35. 4569-4574 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Ishii: "A TREPR Study on the Excited States of Porphynatozic (II) Coordinated by p-Pyridyl Nitroxide" J.Am.Chem.Soc.118. 13079-13080 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J.Fujisawa: "Electron Spin Polarization Generated from Excited Triplet Porphyrins and Stable Radicals" J.Phys.Chem.101. 434-439 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Di Valentin: "A Time-Resolved ENDOR Study of the Photoexcited Triplet State of P680 in Isolated Reaction Centers of Photosystem II" Chem.Phys.Lett.248. 434-437 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J.Fajer: "Molecular Structures of Porphyrin-Quinone Models for Electron Transfer" J.Phys.Chem.100. 14236-14241 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Rubsam: "Nuclear Quadrupole Interaction in Sc@C_<82>" Chem.Phys.Lett.263. 540-544 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Rubsam: "Rotational Dynamics of Metallo-Endofullerenes in Solution" J.Phys.Chem.100. 19310-19314 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Ehara: "Effects of Geometry and Hydrogen Bonding on the T_1 States of 4-Nitropyridine" J.Phys.Chem.99. 2292-2294 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Akiyama: "Origin of An Absorptive ESP Observed in Photochemical Hydrogen Abstraction" J.Phys.Chem.100. 180-183 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Rohrer: "Orieentation-Selected 95 GHz High-Field ENDOR Spectroscopy of Plastoquinone Anion" J.Magn.Reson.Ser A.116. 59-66 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.F.Prisner: "Time-Resolved W-band (95 GHz) EPR Spectroscopy of Zn-substituted Reaction Centers" Chem.Phys.194. 361-370 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Rubsam: "2D EPR IN vestigation of Endohedral La@C_<82> in Solution" Chem.Phys.Lett. 240. 615-621 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Stasko: "EPR Study of fullerene Radicals Generated in Photosensitized TiO_2 Suspensions" J.Chem.Phys.99. 8782-8789 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J.Fujisawa: "ESPT from Excited Triplet Porphyrins to Nitroxide Radical via a Spin Exchange Mechanism" J.Phys.Chem.99. 17082-17084 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N.Hirota: "CIDEP Studies of Photochemical Reactions : Acetone in 2-Propanol and Triethylamine" Bull.Chem.Soc.Jpn.68. 2997-3010 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] R.Hanaishi: "Two-Dimensional Fourier-Transform EPR Nutation Spectroscopy of Spin correlated Radical Pairs" J.Magn.Reson.A116. 196-205 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] R.Hanaishi: "Observation of Spin-Correlated Radical Pairs via Two-Dimensional EPR Nutation Spectroscopy" J.Chem.Phys.103. 4819-4822 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Ishii: "Studies on Monomers and Dimers of Y (III) and La (III) Porphyrin Complexes by means of TREPR" J.Phys.Chem.100. 3839-3846 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Yamauchi: "State Mixing in the Excited Triplet and Singlet States of Fluorine substituted Magnesium Tetraphenylporphines Studied by Optical and Time Resolved EPR" Inorg.Chem.35. 2910-2914 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] R.Hanaishi: "1D and 2D FT-EPR Studies on the Photoinduced Electron Transfer Reaction from Zn Porphtyrin to Duroquinone in CTAC Micellar Solution" Bull.Chem.Soc.69. 1533-1541 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N.Okabe: "Electron Spin Relaxation Studies of La@C_<82> in the Solid State by EPR" J.Phy.Chem.10. 251-262 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] R.Hanaishi: "Two Dimensional FT-EPR Spectroscopy for Spin-Correlated Radical Pairs-Application to Photoinduced Electron Transfer Reaction Between ZnTPPS and DQ in a Micellar Solution" Appl.Magn.Reson.10. 55-69 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Ohkoshi: "Photodissociation of Bis (S-benzyl-1,2-dipenyl-1,2-ethylenedithiolato) metal (Ni, Pd, Pt) Complexes" Inorg.Chem.35. 4569-4574 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Ishi: "A TREPR Study on the Excited States of Tetraphenyl-porphynatozic (II) Coordinated by p-Pyridyl Nitroxide" J.Am.Chem.Soc.118. 13079-13080 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J.Fujisawa: "Electron Spin Polarization Generated from Interaactions between Excitted Triplet Porphyrins and Stable Radicals Studied by TREPR" J.Phys.Chem.101. 434-439 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Di Valentin: "A Time-Resolved ENDOR Study of the Photoexcited Triplet State of P680 in Isolated Reaction Centers of Photosystem II" Chem.Phys.Lett.248. 434-437 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J.Fajer: "Molecular Structures of Porphyrin-Quinone Models for electron Transfer" J.Phys.Chem.100. 14236-14241 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Rubsam: "Nuclear Quadrupole Interaction in Sc@C_<82>" Chem.Phys.Lett.263. 540-544 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Rubsam: "Rotational Dynamics of Metallo-Endofullerenes in Solution" J.Phys.Cehm.100. 19310-19314 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Ishii: "Studies on Monomers and Dimers of Y (III) and La (III) Porphyrin Complexes by means of TREPR" J. Phys. Chem.,. 100. 3839-3846 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Yamauchi: "State Mixing in the Excited Triplet and Singlet States of Magnesium Tetraphenylporphines" Inorg. Chem.,. 35. 2910-2914 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] R.Hanaishi: "1D and 2D FT-EPR Studies on the Photoinduced Electron Transfer" Bull. Chem. Soc. Jpn.,. 69. 1533-1541 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] N.Okabe: "Electron Spin Relaxation Studies of LaC_<82> in the Solid State by EPR" Appl. Magn. Reson.,. 10. 251-262 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] R.Hanaishi: "Two Dimensional FT-EPR Spectroscopy for Spin-Correlated Radical Pairs and Solution" Appl. Magn. Reson.,. 10. 55-69 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Ohkoshi: "Photodissociation of Bis (S-benzly-1,2-diphenyl-1,2-ethylenedithiolato) metal Complexes" Inorg. Chem.,. 35. 4569-4574 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] K.Ishii: "A TREPR Study on the Excited States of Porphynatozic (II) Coordinated by p-Pyridyl Nitroxide" J. Am. Chem. Soc.,. 118. 13079-13080 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] J.Fujisawa: "Electron Spin Polarization Generated from Excited Triplet Porphyrins and Stable Radicals" J. Phys. Chem.,. 101. 434-439 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Di Valentin: "A Time-Resolved ENDOR Study of the Photoexcited Triplet State of P680 in Isolated Reaction Centers of Photosystem II" Chem. Phys. Lett.,. 248. 434-437 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] J.Fajer: "Molecular Structures of Porphyrin-Quinone Models for Electron Transfer" J. Phys. Chem.,. 100. 14236-14241 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Rubsam: "Nuclear Quadrupole Interaction in ScC_<82>" Chem. Phys. Lett,. 263. 540-544 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Rubsam: "Rotational Dynamics of Metallo-Endofullerenes in Solution" J. Phys. Chem.,. 100. 19310-19314 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] K.Ishii: "Studies on Monomers and Dimers of Y(III) Porphyrin Complexes by means of TREPR" J. Phys. Chem.,. (印刷中).

    • Related Report
      1995 Annual Research Report
  • [Publications] N.Okabe: "Electron Spin Relaxation Studies of LaC_<82> in the Solid State by EPR" Appl. Magn. Reson.,. (印刷中).

    • Related Report
      1995 Annual Research Report
  • [Publications] J.Fijisawa: "ESPT from Excited Triplet Porphyrins to Nitroxide Radical via a Spin Exchange Mechanism" J. Phys. Chem.,. 99. 17082-17084 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] N.Hirota: "CIDEP Studies of Photochemical Reactions : Acetone in 2-Propanol and Triethylamine" Bull. Chem. Soc. Jpn.,. 68. 2997-3010 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] R.Hanaishi: "Two-Dimensional Fourier-Transform EPR Nutation Spectroscopy of Spin Correlated Radical Pairs" J. Magn. Reson.,. A116. 196=205 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] R.Hanaishi: "Observation pf Spin-Correlated Radical Pairs via Two-Dimensional EPR Nutation Spectroscopy" J. Chem. Phys.,. 103. 4819-4822 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T.Ehara: "Effects of Geometry and Hydrogen Bonding on the T_1 States of 4-Nitropyridine" J. Phys. Chem.,. 99. 2292-2294 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] K.Akiyama: "Origin of an Absorptive ESP Observed in Photochemical Hydrogen Abstraction" J. Phys. Chem.,. 100. 180-183 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Rohrer: "Orientation-Selected 95GHz High-field ENDOR Spectroscopy of Plastoquinone Anion" J. Magn. Reson. Ser. A.116. 59-66 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T.F.Prisner: "Time-Resolved W-band (95GHz) EPR Spectroscopy of Zn-substituted reaction centers" Chem. Phys.,. 194. 361-370 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Ruebsam: "2D EPR Investigation of Endohedral LaC_<82> in Solution" Chem. Phys. Lett.,. 240. 615-621 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] A.Stasko: "EPR Study of Fullerene Radicals Generated in Photosensitized Ti O_2 Suspensions" J. Chem. Phys.,. 99. 8782-8789 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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