Early excited state dynamics of 6-styryl-substituted pyrylium salts exhibiting dual fluorescence

Anatolio Pigliucci, Peter Nikolov, Abdul Rehaman, Laura Gagliardi, Christopher J. Cramer, Eric Vauthey

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

Abstract

A series of 6-styryl-2,4-diphenylpyrylium salts exhibiting dual fluorescence has been investigated by fluorescence up-conversion in conjunction with quantum chemical calculations. The short-wavelength emission is due to an excited state localized on the pyrylium fragment and the long-wavelength emission arises from a charge-transfer state delocalized over the whole molecule. The two fluorescing states do not exhibit a precursor-successor relationship. The rise time of the short-wavelength fluorescence is smaller than 200 fs, and that of the long-wavelength emission depends on the electron-donating property of the styryl group substituent. The rise is almost prompt with the weaker donors but is slower, wavelength and viscosity dependent with the strongest electron-donating group. A model involving a S 2/S 1 conical intersection is proposed to account for these observations.

Original languageEnglish (US)
Pages (from-to)9988-9994
Number of pages7
JournalJournal of Physical Chemistry A
Volume110
Issue number33
DOIs
StatePublished - Aug 24 2006

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