Photochemistry of Amino-Linked Bichromophoric Anthracenes. Efficient Cyclomerization of 9-(1-Naphthylmethylaminomethyl)anthracene and Adiabatic Cycloreversion of the Cyclomer

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Abstract

The spectral and photochemical properties of the title compound <b>1</b> and bis(9-anthrylmethyl)amine (<b>2</b>) have been investigated. The fluorescence spectrum of <b>1</b> in methylcyclohexane showed an emission from the locally excited state of the anthracene part and a weak broad emission at 410—550 nm from the intramolecular exciplex. The fluorescence quantum yields of <b>1</b> and <b>2</b> decreased along with an increase in the solvent polarity. Both <b>1</b> and <b>2</b> underwent intramolecular [4+4] cycloaddition. The quantum yield of the cyclomerization of <b>1</b> was 0.24 in acidic methanol, while in MeCN the reaction was completely quenched by an intramolecular electron transfer from the amino group to the excited anthracene moiety. Excitation of the cyclomer from <b>1</b> at 285 nm brought about fluorescene from both the locally excited anthracene and the exciplex state, indicating that adiabatic cycloreversion took place on the S<sub>1</sub> potential surface. To investigate the conformations, the crystal structures of <b>1</b> and <b>2</b> were determined and PM3 calculations were performed for <b>1</b>–H<sup>+</sup>. The calculations indicate that a conformer in which the two chromophores are located close to each other has a higher energy then other stable conformers.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 70(4), 869-875, 1997-04-15

    The Chemical Society of Japan

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Codes

  • NII Article ID (NAID)
    10008917731
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • NDL Article ID
    4196835
  • NDL Source Classification
    ZP1(科学技術--化学・化学工業)
  • NDL Call No.
    Z53-B35
  • Data Source
    CJP  NDL  J-STAGE 
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