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

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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 - Oct 15 2014

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ASJC Scopus subject areas

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

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