Photophysical and Photochemical Behavior of Intramolecular Styrene-Amine Exciplexes

Frederick D. Lewis*, G. Dasharatha Reddy, Siegfried Schneider, Michael Gafar

*Corresponding author for this work

Research output: Contribution to journalArticle

52 Scopus citations

Abstract

The photophysical and photochemical behavior of a series of secondary and tertiary u)-(d-styryl)aminoalkanes with one to five methylenes separating the styryl and amino groups has been investigated and compared to the intermolecular reactions of 1 -phenylpropene with secondary and tertiary amines. The tertiary styrylamines form fluorescent intramolecular exciplexes, but fail to undergo intramolecular addition reactions. Both the rate constant for exciplex formation and the stability of the exciplex are dependent upon the length of the polymethylene chain connecting the chromophores. The failure of the tertiary amine exciplexes to undergo intramolecular addition is attributed to an unfavorable exciplex geometry for -C-H transfer to the styrene double bond. While the secondary styrylamines do not form fluorescent exciplexes, the dependence of the styrene singlet lifetime upon the polymethylene chain length is similar to that for the tertiary styrylamines. Intramolecular N-H addition to the styrene double bond results in the formation of two regioisomeric (-phenyl and -benzyl) cyclic amines of different ring size. The regioisomer of larger ring size is favored except in the case in which four methylenes separate the chromophores. The effects of polymethylene chain length, solvent polarity, temperature, and the bulk of the (V-alkyl group upon product yields and ratios are discussed in terms of a mechanism involving singlet exciplex and biradical intermediates.

Original languageEnglish (US)
Pages (from-to)3498-3506
Number of pages9
JournalJournal of the American Chemical Society
Volume113
Issue number9
DOIs
StatePublished - Jan 1 1991

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Photophysical and Photochemical Behavior of Intramolecular Styrene-Amine Exciplexes'. Together they form a unique fingerprint.

  • Cite this