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Dynamics of Photodissociation and Rearrangement of Chemical Bonds in Solution

Research Project

Project/Area Number 02453013
Research Category

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

Allocation TypeSingle-year Grants
Research Field 物理化学一般
Research InstitutionOsaka University

Principal Investigator

OKADA Tadashi  Osaka Univ., Dept. Chemistry Assoc. Prof., 基礎工学部, 助教授 (40029442)

Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥5,700,000 (Direct Cost: ¥5,700,000)
Fiscal Year 1991: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1990: ¥4,300,000 (Direct Cost: ¥4,300,000)
Keywordsphotodissociation / Microscopic Diffusion / tetraarylhydrazine / heterodimer / predissociation / Picosecond Laser Spectroscopy / テトラフェニルヒドラジン / アントラセンヘテロダイマ- / 光シクロ附加 / 環開裂
Research Abstract

l. Photodissociation of Heterodimers of Anthracene and 1, 4-Dihalobebzens in Solution
When a heterodimer is excited in solution, a excited singlet state of anthracene and a ground state of dihalobenzene are produced from the excited singlet state of the heterodimer. We have measured the time-dependence of the fluorescence of heterodimer itself and produced anthracene as well as the time-resolved transient absorption spectra in solution by means of a picosecond laser spectroscopy.
The fluorescence spectrum of anthracene observed by the excitation of heteroexcimer in glass matrix at 77K is shifted to the red about 10nm compared to that of free anthracene, which indicate that a special intermolecular conformation between anthracene and dihalobenzene may be preserved in the low temperature matrix. Dynamical shifts of anthracene fluorescence were detected at room temperature in viscous solvent, cis-decalin.
2. Photodissociation of Tetraphenylhydrazine and Its Derivatives in Solution
The slow N-N bond rupture occurring in the fluorescence state of tetraarylhydrazines has been confirmed by a picosecond time-resolved spectroscopy. The predissociation mechanism from the excited singlet (fluorescent) state to the lower lying dissociative state was proposed.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (42 results)

All Other

All Publications (42 results)

  • [Publications] Y.Sakata: "Observation of Large Orientation Effect on Photoinduced Electron Transfer in Rigid Porphyrin-Quinone Compounds" Chem.Lett.1307-1310 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Morishima: "Photoinduced Charge Separation by Chromophores Encapsulated in the Hydrophobic Compartment of Amphiphilic Polyelectrolytes with Various Aliphatic Hydrocarbones" J.Phys.Chem.95. 6027-6034 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] S.Nishikawa: "Determination of the Bimolecular Rate Constant of Photoinduced Charge Separation in the Energy Gap Region Where the Reaction is Diffusion Controlled-Analysis of the Transient Effect in the Course of Fluorescence Quenching Reaction" Chem.Phys.Lett.185. 237-243 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Hirata: "Vibrational Energy Dissipation Process in Solution:Picosecond Laser Photolysis Studies of Biphenylene" Chem.Phys.Lett.187. 203-207 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Morishima: "Rapid Migration and Trapping of Photoexcited Electronic Energy in Amphiphilic Polyelectrolytes Containing Naphthalene Chromophores and Pyrene Traps" J.Phys.Chem.96. 1990-1994 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H.Miyasaka: "Femtosecond Laser Photolysis Studies on the Cooling Process of Chrysene in the Vibrationally Hot SCC1DD State in Solution" Chem.Phys.Lett.188. 259-264 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Hirata: "Direct Observation of Photodissociation of Tetraphenylhydrazine and its Derivatives in the Solution Phase: Picosecond Study of N-N Bond Rupture in the Fluorescence State" J.Phys.Chem.96. 1517-1520 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T.Okada: "Photoinduced Intramolecular Charge Transfer of TICT and Related Compounds in Femtosecond-Nanosecond Time Regime" Proc.Indian Acad.Sci.(Chem.Sci.),April,1992,. (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 岡田 正: "単バンチによる有機化合物の時間分解蛍光測定" 放射光. 4. 365-370 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 岡田 正: "溶液系の超高速光化学反応初期過程" オプトロニクス,4月号、(1992). (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T.Okada: "Picosecond Laser Photolysis Studies on the Photodissociation Process of Heterodimers of Anthracene and 1,4-Dihalobenzenes in Solution"

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 岡田 正: "時間分解吸収分光(psーfs)第4版実験化学講座7、分光II" 日本化学会編、丸善, 516 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T.Okada: ""Dynamics and Mechanisms of Photoinduces Electron Transfer and Related Phenomena"ed.,N.Mataga,T.Okada,and H.Masuhara" North-Holland, 600 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H.Murakami: ""Dynamics and Mechanisms of Photoinduced Electron Transfer and Related Phenomena" ed.,N.Mataga,T.Okada,and H.Masuhara" North-Holland, 600 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Sakata, H. Tsue, Y. Goto, S. Misumi, T. Asahi, S. Nishikawa, T. Okada, and N. Mataga: "Observation of Large Orientation Effect on Photoinduced Electron Transfer in Rigid Porphyrin-Quinone Compounds" Chem. Lett.1307-1310 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Morishima, Y. Tominaga, M. Kamachi, T. Okada, Y. Hirata, and N. Mataga: "Photoinduced Charge Separation by Chromophores Encapsulated in the Hydrophobic Compartment of Amphiphilic Polyelectrolytes with Various Aliphatic Hydrocarbones" J. Phys. Chem.95. 6027-6034 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] S. Nishikawa, T. Asahi, T. Okada, N. Mataga, and T. Kakitani: "Determination of the Bimolecular Rate Constant of Photoinduced Charge Separation in the Energy Gap Region Where the Reaction is diffusion Controlled-Analysis of the Transient Effect in the Course of Fluoresence Quenching Reaction" Chem. Phys. Lett.185. 237-243 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Hirata and T. Okada: "Vibrational Energy Dissipation Process in Solution : Picosecond Laser Photolysis Studies of Biphenylene" Chem. Phys. Lett.187. 203-207 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Morishima, Y. Tominaga, S. Nomura, M. Kamachi, and T. Okada: "Rapid Migration and Trapping of Photoexcited Electronic Energy in Amphiphilic Polyelectrolytes Containing Naphthalene Chromophores and Pyrene Traps" J. Phys. Chem.96. 1990-1994 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Miyasaka, M. Hagihara, T. Okada, and N. Mataga: "Femtosecond Laser Photolysis Studies on the Cooling Process of Chrysene in the Vibrationally Hot S_1 State in Solution" Chem. Phys. Lett.188. 259-264 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Hirata, M. Ohta, T. Okada, and N. Mataga: "Direct Observation of Photodissociation of Tetraphenylhydrazine and its Derivatives in the Solution Phase : Picosecond Study of N-N Bond Rupture in the Fluorescence State" J. Phys. Chem.96. 1517-1520 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T. Okada: "Photoinduced Intramolecular Charge Transfer of TICT and Related Compounds in Femtosecond-Nanosecond Time Regime" Proc. Indian Acad. Sci. (Chem. Sci.). April. (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T. Okada: "Time-Resolved Fluorescence Spectroscopy of Organic Molecules by Using a Single-Bunch Operation of SR (in Japanese)" Hohsyako. 4. 365-370 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T. Okada: "Primary Processes of Ultrafast Photochemical Reactions in Solution (in Japanese)" Oputoronikusu. April. (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T. Okada, M. Maruyama, M. Ishigaki, H. Okammoto, and M. Kimura: "Picosecond Laser Photolysis Studies on the Photodissociation Process of Heterodimers of Anthracene and 1, 4-Dihalobenzenes in Solution"

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Sakata: "Observation of Large Orientation Effect on Photoinduced Electron Transfer in Rigid PorphyrinーQuinone Compounds" Chem.Lett.1307-1310 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Morishima: "Photoinduced Charge Separation by Chromophores Encapsulated in the Hydrophobic Compartment of Amphiphilic Polyelectrolytes with Various Aliphatic Hydrocarbones" J.Phys.Chem.95. 6027-6034 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] S.Nishikawa: "Determination of the Bimolecular Rate Constant of Photoinduced Charge Separation in the Energy Gap Region Where The Reaction is Diffusion ControlledーAnalysis of the Transient Effect in the Course of Fluorescence Quenching Reaction" Chem.Phys.Lett.185. 237-243 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Hirata: "Vibrational Energy Dissipation Process in Solution:Picosecond Laser Photolysis Studies of Biphenylene" Chem.Phys.Lett.187. 203-207 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Morishima: "Rapid Migration and Trapping of Photoexcited Electronic Energy in Amphiphilic Polyelectrolytes Containing Naphthalene Chromophores and Pyrere Traps" J.Phys.Chem.96. 1990-1994 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] H.Miyasaka: "Femtosecond Laser Photolysis Studies on the Cooling Process of Chrysene in the Vibrationally Hot S_1 State in Solution" Chem.Phys.Lett.188. 259-264 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Hirata: "Direct Observation of Photodissociation of TetraphenyIhydrazine and its Derivatives in the Solution Phase:Picosecond Study of NーN Bond Rupture in the Fluorescence State" J.Phys.Chem.96. 1517-1520 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] T.Okada: "Photoinduced Intramolecular Charge Transfer of TICT and Related Compounds in FemtosecondーNanosecond Time Regime" Proc.Indian Acad.Sci.(Chem.Sci.),April,1992. (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] 岡田 正: "単バンチによる有機化合物の時間分解蛍光測定" 放射光. 4. 365-370 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 岡田 正: "溶液系の超高速光化学反応初期過程" オプトロニクス. 4月号. (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] 岡田 正: "時間分解吸収分光(psーfs) 第4版実験化学講座7、分光II" 日本化学会編、丸善, 516 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] T.Okada: ""Dynamics and Mechanisms of Photoinduced Electron Transfer and Related Phenomena"ed.,N.Mataga,T.Okada,and H.Masuhara" NorthーHolland, 600 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] H.Murakami: ""Dynamics and Mechanisms of Photoinduced Electron Transfer and Related Phenomena"ed.,N.Mataga,T.Okada,and H.Masuhara" NorthーHolland, 600 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] S.Kinoshita: "Solvent Relaxation Effect on Transient HoleーBurning Spectra of Organic Dyes" Chem.Phys.Lett.166. 123-127 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] N.Mataga: "FemtosecondーPicosecond Laser Photolysis Studies on the Photoinduced Charge Separation and Charge Recombination of Produced Ion Pair State of Some Typical Intramolecular Exciplex Compounds in Alkanenitrile Solvents" J.Phys.Chem.94. 1443-1447 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Morishima: "Photoinduced Charge Separation by Hydrophobic Chromophores Compartmentalized in Amphiphilic Polyelectrolytes" J.Phys.Chem.in press.

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Okada: "Dynamics of Intramolecular Electron Transfer in Polar Solvents" Ultrafast Phenomena VII. 397-401 (1990)

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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