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Spin dynamics of organic acids and bases in their nonphosphorescent and short-lived excited triplet states

Research Project

Project/Area Number 11640498
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Physical chemistry
Research InstitutionYokohama National University

Principal Investigator

YAGI Mikio  Yokohama National University, Graduate School of Engineering, Professor, 工学研究院, 教授 (00107369)

Co-Investigator(Kenkyū-buntansha) SEKI Kanekazu  Yokohama National University, Graduate School of Engineering, Associate Professor, 工学研究院, 助教授 (30250103)
Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 2000: ¥1,100,000 (Direct Cost: ¥1,100,000)
Keywordsazastilbene / protonated cation / excited state / electron paramagnetic resonance / zero-field splitting / fluorescence / methylcinnamic acid / deprotonated anion / 一重項酸素分子 / 酸塩基 / 蛍光 / 項間交差
Research Abstract

1. The effects of protonation on the excited states of trans-3-styrylpyridine (StP) and trans-4,4'-dipyridylethylene (DPE) have been studied through measurements of the time-resolved electron paramagnetic resonance (EPR), UV absorption, and fluorescence spectra in methanol-water mixtures at 77 K. From the analysis of these spectra it is concluded that the single protonation appears to have little effect on the zero-field splitting parameters and the anisotropy in the sublevel populating rates of the lowest excited triplet (T_1) states of StP and DPE. The decay rate constants of the fluorescent states decrease and fluorescence quantum yields increase on single protonation. These experimental results suggest that the single protonation causes a decrease in the intersystem crossing rates for the three T_1 sublevels. These results are explained in terms of the vibronic mixing between the ^1nπ^* and ^1ππ^* states in the lowest excited singlet state.
2. The esters of trans-p-methoxycinnamic acid are the most widely used UV absorbers in cosmetic sunscreens. To be effective as a UV protective compound in skin-care sunscreens, the UV absorber must be able to harmlessly transform the absorbed UV energy into vibrational energy. The deactivation mechanism of trans-cinnamic acids (CAs) and their esters have been an object of continuous interest for many years. However, the property of the T_1 states of CAs and their esters is poorly known. This is because of their weakly phosphorescent character and short T_1 lifetimes. In the present research, the effects of deprotonation on the excited states of trans-p-methylcinnamic acid have been studied through measurements of the time-resolved EPR and fluorescence in rigid organic glasses and in stretched poly(vinyl alcohol) films at 77 K. The deprotonation appears to have little effect on the zero-field splitting parameters. However, the triplet sublevel kinetics changes on deprotonation.

Report

(3 results)
  • 2001 Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] 八木幹雄: "Photoexcited triplet states of organic molecules in ionic forms"Trends m Photochenustry & Photobiology. 6. 99-112 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 樋口治郎: "Electron paramagnetic resonance study on the triplet species produced from 2-nitrobiphenyl derivatives by UV irradiation"J. Photochemistry and Photobiology, A: Chemistry. 124(1,2). 53-65 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 落水朋樹: "Rate constants for the reactions of CN with C_6-C_8 unsaturated hydrocarbons: the relations between the reaction rates and the molecular lengths"Chemical Physics Letters. 313(3,4). 451-455 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 八木幹雄: "Optical and time-resolved EPR studies of the excited states of azastilbenes and their protonated cations"Applied Magnetic Resonance. 18(3). 385-395 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 船山智代: "Studies of the lowest excited triplet state of 3,3'-biisoquinoline(dicyano)platinum(II)-[Pt(CN)_2(i-biq)]by means of time-resolved electron paramagnetic resonance and optical spectroscopy"Bulletin of the Chemical Society of Japan. 73(7). 1541-1550 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 樋口治郎: "Electron paramagnetic resonance studies of the lowest triplet states of polyphenyl molecules in rigid glasses"Journal of Physical Chemistry A. 105(25). 6084-6091 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 関根あき子: "4-Nitro-9, 10-dihydrophenanthrene and a polymorphic form of 4-nitrophenanthrene"Acta Crystallographica C. 57(12). 1462-1464 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 山元一郎: "Time-resolved EPR studies of the excited triplet states of p-methylcinnamic acid and its deprotonated anion"Proceedings of the Third Asia-Pacific EPR/ESR Symposium, 2001, Kobe, Japan, Elsevier, Amsterdam. (印刷中). (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Mikio Yagi: "Photoexcited triplet states of organic molecules in ionic forms"Trends in Photochemistry & Photobiology. 6. 99-112 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Jiro Higuchi: "Electron paramagnetic resonance study on the triplet species produced from 2-nitrobiphenyl derivatives by UV irradiation"J. Photochemistry and Photobiology, A : Chemistry. 124 (1, 2). 53-65 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Tomoki Ochimizu: "Rate constants for the reactions of CN with C_6-C_8 unsaturated hydrocarbons : the relations between the reaction rates and the molecular lengths"Chemical Physics Letters. 313 (3, 4). 451-455 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M. Yagi: "Optical and time-resolved EPR studies of the excited states of azastilbenes and their protonated cations"Applied Magnetic Resonance. 18 (3). 385-395 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Tomoyo Funayama: "Studies of the lowest excited triplet state of 3,3'-biisoquinoline-(dicyano)- platinum(II)[Pt(CN)_2(i-biq)] by means of time-resolved electron paramagnetic resonance and optical spectroscopy"Bulletin of the Chemical Society of Japan. 73 (7). 1541-1550 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Jiro Higuchi: "Electron paramagnetic resonance studies of the lowest triplet states of polyphenyl molecules in rigid glasses"Journal of Physical Chemistry A. 105 (25). 6084-6091 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Akiko Sekine: "4-Nitro-9,10-dihydrophenanthrene and a polymorphic form of 4-nitrophenanthrene"Acta Crystallographica C. 57 (12). 1462-1464 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Ichiro Yamamoto: "Time-resolved EPR studies of the excited triplet states of p-methylcinnamic acid and its deprotonated anion""Proceedings of the Third Asia-Pacific EPR/ESR Symposium, 2001, Kobe, Japan", Elsevier, Amsterdam. (in press). (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 八木幹雄: "Optical and time-resolved EPR studies of the excited states of azastilbenes and their protonated cations"Applied Magnetic Resonance. 18(3). 385-395 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 船山智代: "Studies of the lowest excited triplet state of 3,3'-biisoquinoline (dicyano) platinum (II)-[Pt (CN) _2 (i-biq)] by means of time-resolved electron paramagnetic resonance and optical spectroscopy"Bulletin of the Chemical Society of Japan. 73(7). 1541-1550 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 八木 幹雄: "Photoexcited triplet states of organic molecules in ionic forms"Trends in Photochemistry & Photobiology. 6. 99-112 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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