• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

CONTROL OF PHOTOCHEMICAL REACTIONS BY HYDROGEN BONDING

Research Project

Project/Area Number 08640666
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionUNIVERSITY OF TSUKUBA

Principal Investigator

ARAI Tatsuo  UNIVERSITY OF TSUKUBA,DEPARTMENT OF CHEMISTRY PROFESSOR, 化学系, 教授 (50151139)

Project Period (FY) 1996 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1997: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1996: ¥1,000,000 (Direct Cost: ¥1,000,000)
KeywordsPHOTOISOMERIZATION / HYDRGEN TRANSFER / TAUTOMERIZATION / EXCITED STATE / FLUORESCENCE / 水素結合 / 水素原子移動 / 異性化 / レーザーホトリシス
Research Abstract

We have investigated the effect of hydrogen bonding to control the efficiency and the mode of photochemical isomerization. Furthermore, novel photoinduced hydrogen atom transfer to give the tautomer have been studied.
We found a co-operative effect of intramolecular hydrogen bonding and solvent to control the efficiency and the selectivity of photoisomerization in an olefin with a pyrrole ring and a quinoxaline ring (I). In benzene, I underwent one-way trans*cis photoisomerization due to the intramolecular hydrogen bonding. Thus, cis-I did not undergo cis-to-trans isomerization, but undergo intramolecular hydrogen atom transfer to give the tautomer as revealed by the observation of the fluorescence emission with considerably large Stokes-shift. One the other hand, the cis-to-trans isomerization prevails over trans-to-cis isomerization in methanol by making an intermolecular hydrogen bonding.
In 2'-hydroxychalcone (II), we found a novel one-way cis*trans isomerization induced by the intramolecular hydrogen atom transfer in the triplet state based on the results by laser transient spectroscopy.
We also found an novel effect of formyl group on the behavior of intramolecularly hydrogen bonded compound ; the introduction of the formyl group increased the efficiency of hydrogen atom transfer to give the tautomer. Thus, 2 [2- (2-pyridy) ethenyl] pyrrole-5-carboxaldehyde III with formyl group at the pyrrole ring exhibited considerably high quantum efficiency of fluorescence emission from the tautomer produced by intramolecular hydrogen atom transfer, although the intersystem crossing to the triplet state is also accelerated as revealed from the observation of the quantum chain process.

Report

(3 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • Research Products

    (15 results)

All Other

All Publications (15 results)

  • [Publications] 新井 達郎: "Novel solvent effect on highly selective photochemical isomerization of 2-[2-(2-pyrrolyl)ethenyl]quinoxaline" Chemistry Letters. 335-336 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 新井 達郎: "Direct observation of the photoinduced hydrogen atom transfer in 2^1-hydroxychalcone" Chemistry Letters. 339-340 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 新井 達郎: " Novel photochemial behavior of olefin with a pyrrole ring and a phenanthroline ring controlled by hydrogen bonding" Tetrahedron Letters. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Arai and Y.Maeda: "Novel solvent effect on highly selective photochemical isomerization of 2- [2- (2-pyrrolyl) ethenyl] quinoxaline" Chemistry Letters. No.4. 335-336 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Arai and Y.Norikane: "Direct observation of the photoinduced hydrogen atom transfer in 2'-hydroxychalcone." Chemistry Letters. No.4. 339-340 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Yang and T.Arai: "Novel photochemial behavior of olefin with a pyrrole ring and a phenanthroline ring controlled by hydrogen bonding" Tetrahedron Letters. (in press.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 新井達郎: "Novel solvent effect on highly selective photochemical isomerization of 2-【2-(2-pyrrolyl)ethenyl】quinoxaline" Chemistry Letters. 4号. 335-336 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 新井達郎: "Direct observation of the photoinduced hydrogen atom transfer in 2'-hydroxchalcone" Chemistry Letters. 4号. 339-340 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 新井達郎: "Novel photochemial behavior of olefin with a pyrrole ring and a phenanthroline ring controlled by hydrogen bonding" Terahedron Letters. (印刷中).

    • Related Report
      1997 Annual Research Report
  • [Publications] Tatsuo ARAI: "Photochemical behavior of 2-[2-(2-pyridyl)ethenyl]indole on triplet sensitization.Spin multiplicity dependence of the isomerization modes of an intramolecularly hydrogen bonded compound," J.Photochem.Photobiol.A : Chem.96. 65-69 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Tatsuo ARAI: "Photochemical isomerization around the C=N double bonds of N-methoxy-1-(1-pyrenyl)methanimines in the excited states" J.Photochem.Photobiol.A : Chem.97. 133-138 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Tatsuo ARAI: "One-way cis→trans photoisomerization of azulenylethenes" J.Photochem.Photobiol.A : Chem.(印刷中).

    • Related Report
      1996 Annual Research Report
  • [Publications] Tatsuo ARAI: "Preferential association of 7-azaindole dimer in acetonitrile studied by mass spectrometry" Chem.Lett.(印刷中).

    • Related Report
      1996 Annual Research Report
  • [Publications] Tatsuo ARAI: "Novel solvent effect on highly selective photochemical isomerization of 2-[2-(2-pyrrolyl)ethenyl]quinoxaline" Chem.Lett.(印刷中).

    • Related Report
      1996 Annual Research Report
  • [Publications] Tatsuo ARAI: "Direct observation of the photoinduced hydrogen atom transfer in 2'-hydroxychalcone" Chem.Lett.(印刷中).

    • Related Report
      1996 Annual Research Report

URL: 

Published: 1996-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi