Evidence for the rapid conversion of primary photoexcitations to triplet states in seleno- and telluro- analogues of poly(3-hexylthiophene)

Ryan D. Pensack, Yin Song, Theresa M. McCormick, Ashlee A. Jahnke, Jon Hollinger, Dwight S. Seferos, Gregory D. Scholes

Research output: Contribution to journalArticle

34 Scopus citations

Abstract

Broadband pump-probe spectroscopy is used to examine the ultrafast photophysics of the π-conjugated polymers poly(3-hexylselenophene) (P3HS) and poly(3-hexyltellurophene) (P3HTe) in solution. An excited-state absorption feature that we attribute to a transition in the triplet manifold appears on the picosecond time scale. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations support this assignment. The formation of triplets is consistent with significant fluorescence quenching observed in solutions of the neat polymers. Triplet formation occurs in ∼26 and ∼1.8 ps (upper limit) for P3HS and P3HTe, respectively. The successive decrease in fluorescence quantum efficiency and triplet formation time are consistent with intersystem crossing facilitated by the heavier selenium and tellurium atoms. These results strongly suggest that primary photoexcitations are rapidly converted into triplet states in P3HS and P3HTe.

Original languageEnglish (US)
Pages (from-to)2589-2597
Number of pages9
JournalJournal of Physical Chemistry B
Volume118
Issue number9
DOIs
StatePublished - Mar 6 2014
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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