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Spectroscopic study on specific intermolecular interactions in aromatic biomolecules in the isolated state.

Research Project

Project/Area Number 15350015
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Physical chemistry
Research InstitutionKYUSHU UNIVERSITY

Principal Investigator

SEKIYA Hiroshi  Kyushu University, Department of Chemistry, Faculty of Sciences, Professor, 大学院・理学研究院, 教授 (90154658)

Co-Investigator(Kenkyū-buntansha) OHASHI Kazuhiko  Kyushu University, Department of Chemistry, Faculty of Sciences, Associate Professor, 大学院・理学研究院, 助教授 (80213825)
SAKOTA Kenji  Kyushu University, Department of Chemistry, Faculty of Sciences, Research Associate, 大学院・理学研究院, 助手 (80346767)
Project Period (FY) 2003 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥13,000,000 (Direct Cost: ¥13,000,000)
Fiscal Year 2004: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2003: ¥11,400,000 (Direct Cost: ¥11,400,000)
Keywordsbiomolecules / hydrogen-bonded cluster / double-proton transfer / gas phase / electronic spectrum / picosecond time-resolved study / cooperative effect / dimer / 水素結合 / 孤立状態 / エキシトン相互作用 / 7-アザインドールダイマー / プロトン移動 / 超音速ジェット / トンネル効果 / 励起状態ダイナミクス
Research Abstract

Structures and the excited-state dynamics of hydrogen bonded molecules in supersonic jet expansion have been studied by both the frequency domain and time-domain measurements. We have measured hole-burning spectra of various deuterated isotomers of the hydrogen bonded 7-azaindole dimer. The spectra show that the exciton resonance interaction in the lowest excited state of the 7-azaindole dimer should be treated as a weak coupling limit of the exciton theory. The hole-burning spectra suggest that the vibronic states with short and long lifetimes are excited in the femtosecond time-resolved experiments by Zewail's group, providing bi-exponential decay profiles. The biexponential decay profiles had been a strong evidence of the stepwise excited-state double-proton transfer (ESDPT). However, we have found that the decay profiles excited by picoseond pulse are fitted with single-exponential functions. This result clearly shows that ESDPT occurs by the concerted mechanism. The dispersed fluo … More rescence spectra are measured for the undeuterated and deuterated 7-azaindole dimers. A remarkable H/D isotope effects on the reaction rate has been detected. We have found a cooperative nature of the ESDPT reaction.
The effect of substitution on the ESDPT reaction has also been studied. The substitution of the methyl group at the 3-position of the 7-azaindole does not affect the ESDPT rate, but the substitution of the Cl atom or the dimethylamino group at the 4-position significantly decrease the ESDPT rate due to the weakening of the intermolecular hydrogen-bonds.
We also measured various hydrogen bonded clusters in the neutral and ionic states to investigate the relation between the structure and dynamics. For example, we have examined the excited-state proton transfer of the 7-azaindole-(H_2O)_n(n=1-3). Previous report by Castleman et al. with femtosecond spectroscopy concluded that the excited-state proton transfer occurs in 7-azaindole-(H_20)_n(n=2-4). However, no red-shifted fluorescence has been observed in 7-azaindole-(H_2O)_n(n=1-3), indicating that the excited-state proton transfer is inhibited. Less

Report

(3 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • Research Products

    (25 results)

All 2005 2004 Other

All Journal Article (18 results) Publications (7 results)

  • [Journal Article] Dispersed fluorescence spectra of jet-cooled 7-azaindole-(H_2O)_n(n=1-3) : Does photoinduced excited-state proton transfer occur or not?2005

    • Author(s)
      K.Sakota, H.Sekiya et al.
    • Journal Title

      Chem.Phys.Lett. 406

      Pages: 34-38

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Excited-state double-proton transfer in the (3-methyl-7-azaindole)-(7-azaindole) hetero-dimer in the gas phase2005

    • Author(s)
      Y.Komoto, K.Sakota, H.Sekiya et al.
    • Journal Title

      Chem.Phys.Lett. 406

      Pages: 15-19

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Excited-state double-proton transfer in the 7-azaindole dimer in the gasphase. 2. Cooperative nature of double-proton transfer revealed by H/D kinetic isotopic effects2005

    • Author(s)
      K.Sakota, H.Sekiya
    • Journal Title

      J.Phys.Chem.A 109

      Pages: 2722-2727

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Excited-state double-proton transfer in the 7-azaindole dimer in the gas phase. 1. Evidence of complete localization in the lowest excited electronic state of asymmetric isotonomers2005

    • Author(s)
      K.Sakota, H.Sekiya
    • Journal Title

      J.Phys.Chem.A 109

      Pages: 2718-2721

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Dispersed fluorescence spectra of jet-cooled 7-azaindole-(H_2O)_n(n=1-3) : Does photoinduced excited-state proton transfer occur or not?2005

    • Author(s)
      A.Hara, K.Sakota, M.Nakagaki, H.Sekiya
    • Journal Title

      Chem.Phys.Lett. 407(1-3)

      Pages: 34-38

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Excited-state double-proton transfer in the(3-methyl-7-azaindole)-(7-azaindole) hetero-dimer in the gas phase2005

    • Author(s)
      Y.Komoto, K.Sakota, H.Sekiya
    • Journal Title

      Chem.Phys.Lett. 406(1-3)

      Pages: 15-19

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Excited-state double-proton transfer in the 7-azaindole dimer in the gas phase. 1.Evidence of complete localization in the lowest excited electronic state of asymmetric isotopomers2005

    • Author(s)
      K.Sakota, H.Sekiya
    • Journal Title

      J.Phys.Chem.A 109(12)

      Pages: 2718-2821

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Excited-state double-proton transfer in the 7-azaindole dimer in the gas phase. 2.Cooperative nature of double-proton transfer revealed by H/D kineticisotopic effects2005

    • Author(s)
      K.Sakota, H.Sekiya
    • Journal Title

      J.Phys.Chem.A 109(12)

      Pages: 2722-2727

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Excited-state double-proton transfer in the (3-methyl-7-azaindole)-(7-azaindole) heterodimer in the gas phase2005

    • Author(s)
      A.Hara et al.
    • Journal Title

      Chemical Physics Letters (in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Excited-state double-proton transfer in the 7-azaindole dimer in gas phase 1. Evidence of complete localization in the lowest excited electronic state of asymmetric istopomers2005

    • Author(s)
      K.Sakota, H.Sekiya
    • Journal Title

      Journal of Physical Chemistry A (in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Excited-state double-proton transfer in the 7-azaindole dimer in gas phase 2. Cooperative nature of double-proton transfer revealed by H/D kinetic isotopic effects2005

    • Author(s)
      K.Sakota, H.Sekiya
    • Journal Title

      Journal of Physical Chemistry A (in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Dispersed fluorescence spectra of jet-cooled 7-azaindole-(H_2O)_n(n=1-3). Does photoinduced excited-state proton transfer occur or not?2005

    • Author(s)
      A.Hara et al.
    • Journal Title

      Chemical Physics Letters (in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Electronic spectra of jet-cooled 3-mathyl-7-azaindole dimer. Symmetry of the lowest excited electronic state and double-proton transfer2004

    • Author(s)
      A.Hara, K.Sakota, H.Sekiya
    • Journal Title

      J.Phys.Chem.A 108

      Pages: 10789-10793

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Ultrafast excited-state dynamics in photochromic N-salicylideneaniline studied by femtosecond time-resolved REMPI spectroscopy2004

    • Author(s)
      C.Okabe, T.H.Sekiya et al.
    • Journal Title

      J.Chem.Phys. 121

      Pages: 9436-9444

    • NAID

      120005608120

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Electronic spectra of jet-cooled 3-mathyl-7-azaindole dimer. Symmetry of the lowest excited electronic state and double proton transfer2004

    • Author(s)
      A.Hara, Y.Komoto, K.Sakota, R.Miyoshi, Y.Iuokuchi, K.Ohashi, K.Kubo, E.Yamamoto, A.Mori, N.Nishi, H.Sekiya
    • Journal Title

      J.Phys.Chem.A 108(49)

      Pages: 10789-10793

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Electronic spectra of jet-cooled 3-methyl-7-azaindole dimer. Symmetry of the lowest excited electronic state and double-proton transfer2004

    • Author(s)
      Y.Komoto et al.
    • Journal Title

      Journal of Physical Chemistry A 108・49

      Pages: 10789-10793

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Ultrafast excited-state dynamics in photochronic N-salicylideneaniline studied by femtosecond time-resolved REMPI spectroscopy2004

    • Author(s)
      C.Okabe et al.
    • Journal Title

      Journal of Chemical Physics 121・19

      Pages: 9436-9442

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Excited-State Double-Proton Transfer in the 7-Azaindole Dimer in the Gas Phase. 3.Reaction Mechanism Studied by Picosecond Time-Resolved REMPI Spectroscopy

    • Author(s)
      K.Sakota, C.Okabe, N.Nishi, H.Sekiya
    • Journal Title

      J.Phys.Chem.A 109(25)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] K.Sakota et al.: "Excited-state double-proton transfer dynamics of deuterated 7-azaindole dimers in a free jet studied by hole-burning spectroscopy"Physical Chemistry Chemical Physics. 6・1. 32-36 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Mori et al.: "Effects of intermolecular interaction on proton tunneling : Theoretical study on two-dimensional potential energy surfaces for 9-hydroxyphenalenone-CO2/H2O complexes"Journal of Chemical Physics. 119・8. 4159-4165 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Honkawa et al.: "Infrared spectra and structures of aniline(+)-furan and aniline(+)-phenol. Preference between n-type and s-type hydrogen-bonded structures"Chemical Physics Letters. 376・1-2. 244-250 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] C.Okabe et al.: "Picosecond time-resolved stokes and anti-stokes Raman studies on the photochromic reactions of diarylethene derivatives"Journal of Physical Chemistry A. 107・28. 5384-5390 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Sakota, H.Sekiya: "One-color two-photon and three-photon PFI-ZEKE spectra of trans-butadiene and trans-hexatriene"Physical Chemistry Chemical Physics. 5・14. 2854-2957 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] A.Goldberg et al.: "Rotational isomerization of dithienylethenes : A study on the mechanism determining quantum yield of cyclization reaction"Journal of Physica Chemistry A. 107・25. 4982-4988 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Miyazaki et al.(共著): ""Atom tunneling on molecular structure", in Atom tunneling phenomena in physics, chemistry and biology"Springer Vertrag. 31/313 (2004)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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