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1991 Fiscal Year Final Research Report Summary

Pulsed EPR and ENDOR Studies of Photochemical Reaction Dynamics of Transition Metal Complexes

Research Project

Project/Area Number 02453036
Research Category

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

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionTOHOKU UNIVERSITY

Principal Investigator

IWAIZUMI Masamoto  Tohoku University. Institute for Chemical Reaction Science, Professor, 反応化学研究所, 教授 (70006295)

Co-Investigator(Kenkyū-buntansha) OHBA Yasunori  Tohoku University. Institute for Chemical Reaction Science, Research Assistant, 反応化学研究所, 助手 (10176985)
YAMAUCHI Seigo  Tohoku University. Institute for Chemical Reaction Science, Associate Professor, 反応化学研究所, 助教授 (10127152)
Project Period (FY) 1990 – 1991
KeywordsPulsed EPR / FT-EPR / Time-Resolved EPR / Time-Resolved ENDOR / Photochemistry of Metal Complexes
Research Abstract

The pulsed EPR spectroscopy has higher time resolution and sensitivity than CW-time resolved EPR spectroscopy. We have attempted to apply such a powerful spectroscopy to study of transient processes of photochemical reactions of metal complexes as the following.
1. The home made electron spin echo and spin echo ENDOR instrument was modified on the following points so as to enable study of photochemical reactions. (1) Synchronous operation of laser light and microwave pulses and data accumulation. (2) Preparation of bridged loop gap resonator to get higher time resolution and sensitivity. (3) Preparation of highly stable microwave oscillator system. (4) Microwave pulse generator with four channels of different phases which enables measurements of FT-EPR spectra.
2. Efficiency of the prepared pulsed EPR spectrometer was compared with that of the CW-time resolved EPR spectrometer and it was confirmed that the pulse method has much higher time resolution and sensitivity, but it has still some problems to apply it for studies of reaction systems which produces paramagnetic intermediate species containing spin centers in the transition metal ions.
3. By using the spectrometer, the following photochemical reactions have been investigated. (1) Photoinduced electron transfer reactions between zinc porphyrins and quinones. (2) Photoreduction reaction of bis(diethyldithiocarbamato)copper(II) and its related complexes. (3) Hyperfine coupling interactions in the photoexcited triplet state of porphyrins by the time resolved ENDOR method.

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] Minoru Hanaya: "EPR Studies of Photochemical Reactions of [MeCpMo(CO)_3]_2with Quinones." J.Organomet.Chem.417. 407-420 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Seigo Yamauchi: "A Time-Resolved Electron Paramagnetic Resonance Study on the Photo-induced Electron Transfer Reactions from Metalloporphyrins to Quinones." J.Photochem.Photobiol.A:Chem.65. 177-182 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Minoru Hanaya: "EPR Studies of Photochemical Reactions of Hexacarbonylbis(η5-2,4-cyclopentadien-1-y1)ditungsten,[CpW(CO)_3]_2,with Quinones." J.Organomet.Chem.435. 337-345 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Miharu Ohtani: "Direct Observation of the Intermediate Species in the Photodissociation of Bis(S-benzy1-1,2-dipheny1-1,2-ethy-lenedithiolato)nickel by Time-Resolved EPR and UV-Vis Absorption Spectroscopy." Inorg.Chem.31. 3873-3874 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 大庭 裕範: "パルスEPR用4位相マイクロ波パルス発生器の試作" 東北大反応研報告. 33-37 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yasunori Ohba: "A New Technique for Accurate Measurements and Adjustment of the Phase of the Microwave Pulse in the Pulsed EPR Spectroscopy." J.Magn.Reson.(1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 山内 清語(分担執筆): "時間分解ESRとバイオ・高分子-光合成モデル系への応用-バイオ・高分子における物理化学計測とその応用-" 学会出版センター, 21 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Minoru Hanaya: "EPR Studies of Photochemical Reactions of [MeCpMo(CO)_3]_2 with Quinones." J. Organomet. Chem.417. 407-420 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Seigo Yamauchi: "A Time-Resolved Electron Paramagnetic Resonance Study on the Photo-induced Electron Transfer Reactions from Metalloporphyrins to QuinOnes." J. Photochem. Photobiol. A: Chem.65. 177-182 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Minoru Hanaya: "EPR Studies of Photochemical Reactions of Hexacarbonylbis(eta^5-2,4-cyclopentadien-1-yl)ditungsten, [CpMo(CO)_3]_2 with Quinones." J. Organomet. Chem.435. 337-345

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Miharu Ohtani: "Direct Observation of the Intermediate Species in the Photodissociation of Bis(S-benzyl-1,2-diphenyl-1,2-ethylenedithiolato)nickel by Time-Resolved EPR and UV-Vis Absorption Spectroscopy." Inorg. Chem.31. 3873-3874 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yasunori Ohba: "A New Technique for Accurate Measurements and Adjustment of the Phase of the Microwave Pulse in the Pulsed EPR Spectroscopy." J. Magn. Reson.(1993)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1994-03-18  

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