Excimer formation in cofacial and slip-stacked perylene-3,4

9,10-bis(dicarboximide) dimers on a redox-inactive triptycene scaffold

Eric A. Margulies, Leah E. Shoer, Samuel W. Eaton, Michael R Wasielewski

Research output: Contribution to journalArticle

71 Citations (Scopus)

Abstract

Excitation energy transfer in perylene-3,4:9,10-bis(dicarboximide) (PDI) aggregates is of interest for light-harvesting applications of this strongly absorbing and π-π stacking chromophore. Here we report the synthesis and characterization of two PDI dimers in which the chromophores are covalently linked by a redox-inactive triptycene bridge in orientations that are cofacial (1) and slip-stacked along their N-N axes (2). Femtosecond transient absorption experiments on 1 and 2 reveal rapid exciton delocalization resulting excimer formation. Cofacial π-π stacked dimer 1 forms a low-energy excimer state absorption (λmax = 1666 nm) in τ = ∼2 ps after photoexcitation. Inserting a phenyl spacer on the bridge to generate a slip-stacked PDI-PDI geometry in 2 results in a less stable excimer state (λmax = 1430 nm), which forms in τ = ∼12 ps due to decreased electronic coupling. The near-infrared (NIR) excimer absorption of cofacial dimer 1 is ∼120 meV lower in energy than that of slip-stacked dimer 2, further highlighting electronic differences between these states.

Original languageEnglish
Pages (from-to)23735-23742
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume16
Issue number43
DOIs
Publication statusPublished - Nov 21 2014

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Perylene
excimers
Scaffolds
Dimers
slip
dimers
Chromophores
chromophores
Excitation energy
Photoexcitation
photoexcitation
electronics
Energy transfer
spacers
energy transfer
excitons
Infrared radiation
Geometry
Oxidation-Reduction
triptycene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)

Cite this

Excimer formation in cofacial and slip-stacked perylene-3,4 : 9,10-bis(dicarboximide) dimers on a redox-inactive triptycene scaffold. / Margulies, Eric A.; Shoer, Leah E.; Eaton, Samuel W.; Wasielewski, Michael R.

In: Physical Chemistry Chemical Physics, Vol. 16, No. 43, 21.11.2014, p. 23735-23742.

Research output: Contribution to journalArticle

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