Infrared and ultraviolet laser spectroscopy of jet-cooled substituted salicylic acids; substitution effects on the excited state intramolecular proton transfer in salicylic acid

E. Abd El-Hakam Abou El-Nasr, Asuka Fujii, T. Ebata, N. Mikami

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

Substitution effects on the excited state intramolecular proton transfer (ESIPT) in the salicylic acid (SA) frame were studied by electronic and infrared spectroscopy of jet-cooled 5-methoxylsalicylic acid (5-MeOSA), 5-methylsalicylic acid (5-MeSA), 5-fluorosalicylic acid (5-FSA), 6-fluorosalicylic acid (6-FSA), and methyl salicylate (MS). Infrared spectra were measured in the 3 μm region for both the electronic ground (S 0) and first excited (S1) states. The electronic excitation/emission spectra of 5-MeSA and 6-FSA showed the typical spectral features of ESIPT, which have been found in the spectra of SA. On the other hand, 5-MeOSA and 5-FSA exhibit a mirror-image relation between their excitation and emission spectra, which has been regarded as a result of the suppression of ESIPT. Despite such a remarkable difference among the electronic spectra, IR spectroscopy shows that a drastic change of the phenolic OH stretching vibration does occur upon electronic excitation of all substituted SAs, that is, the phenolic OH band of all the SAs disappears from the 3 μm region, indicating a large elongation of the phenolic O-H bond (over 0.1 Å) in S1. This result means that the intramolecular hydrogen bond strength is remarkably enhanced by electronic excitation in all the substituted SAs. Substitution effects on ESIPT in dimers are also discussed.

Original languageEnglish
Pages (from-to)1561-1572
Number of pages12
JournalMolecular Physics
Volume103
Issue number11-12
DOIs
Publication statusPublished - 2005 Jun 1

ASJC Scopus subject areas

  • Biophysics
  • Molecular Biology
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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