Ultrafast Exciton Delocalization, Localization, and Excimer Formation Dynamics in a Highly Defined Perylene Bisimide Quadruple π-Stack

Christina Kaufmann, Woojae Kim, Agnieszka Nowak-Król, Yongseok Hong, Dongho Kim, Frank Würthner

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92 Citations (Scopus)


An adequately designed, bay-tethered perylene bisimide (PBI) dimer Bis-PBI was synthesized by Pd/Cu-catalyzed Glaser-type oxidative homocoupling of the respective PBI building block. This newly synthesized PBI dimer self-assembles exclusively and with high binding constants of up to 106 M-1 into a discrete π-stack of four chromophores. Steady-state absorption and emission spectra show the signatures of H-type excitonic coupling among the dye units. Broadband fluorescence upconversion spectroscopy (FLUPS) reveals an ultrafast dynamics in the optically excited state. An initially coherent Frenkel exciton state that is delocalized over the whole quadruple stack rapidly (τ = ∼200 fs) loses its coherence and relaxes into an excimer state. Comparison with Frenkel exciton dynamics in PBI dimeric and oligomeric H-aggregates demonstrates that in the quadruple stack coherent exciton propagation is absent due to its short length of aggregates, thereby it has only one relaxation pathway to the excimer state. Furthermore, the absence of pump-power dependence in transient absorption experiments suggests that multiexciton cannot be generated in the quadruple stack, which is in line with time-resolved fluorescence measurements.

Original languageEnglish
Pages (from-to)4253-4258
Number of pages6
JournalJournal of the American Chemical Society
Issue number12
Publication statusPublished - 2018 Mar 28

Bibliographical note

Funding Information:
The research at the Universitat Wurzburg was supported by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) within the research unit FOR 1809. The research at Yonsei University was supported by the Global Research Laboratory Program (2013K1A1A2A02050183) funded by the Ministry of Science, ICT & Future, Korea.

Publisher Copyright:
© 2018 American Chemical Society.

All Science Journal Classification (ASJC) codes

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


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