Solvent-templated folding of perylene bisimide macrocycles into coiled double-string ropes with solvent-sensitive optical signatures

Peter Spenst, Ryan M. Young, Brian T. Phelan, Michel Keller, Jakub Dostal, Tobias Brixner, Michael R Wasielewski, Frank Wurthner

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

A series of semirigid perylene bisimide (PBI) macrocycles with varied ring size containing two to nine PBI chromophores were synthesized in a one-pot reaction and their photophysical properties characterized by fluorescence, steadystate, and transient absorption spectroscopy as well as femtosecond stimulated Raman spectroscopy. These macrocycles show solvent-dependent conformational equilibria and excited-state properties. In dichloromethane, the macrocycles prevail in wide-stretched conformations and upon photoexcitation exhibit symmetry-breaking charge separation followed by charge recombination to triplet states, which photosensitize singlet oxygen formation. In contrast, in aromatic solvents folding of the macrocycles with a distinct odd-even effect regarding the number of PBI chromophore units was observed in steady-state and time-resolved absorption and fluorescence spectroscopy as well as femtosecond stimulated Raman spectroscopy. These distinctive optical properties are attributable to the folding of the even-membered macrocycles into exciton-vibrational coupled dimer pairs in aromatic solvents. Studies in a variety of aromatic solvents indicate that these solvents embed between PBI dimer pairs and accordingly template the folding of even-membered PBI macrocycles into ropelike folded conformations that give rise to solvent-specific exciton-vibrational couplings in UV-vis absorption spectra. As a consequence of the embedding of solvent molecules in the coiled double-string rope architecture, highly solvent specific intensity ratios are observed for the two lowest-energy exciton-vibrational bands, enabling assignment of the respective solvent simply based on the absorption spectra measured for the tetramer macrocycle.

Original languageEnglish
Pages (from-to)2014-2021
Number of pages8
JournalJournal of the American Chemical Society
Volume139
Issue number5
DOIs
Publication statusPublished - Feb 8 2017

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Excitons
Raman Spectrum Analysis
Chromophores
Absorption spectroscopy
Dimers
Raman spectroscopy
Conformations
Absorption spectra
perylene bisimide
Singlet Oxygen
Photoexcitation
Methylene Chloride
Fluorescence Spectrometry
Dichloromethane
Fluorescence spectroscopy
Excited states
Genetic Recombination
Spectrum Analysis
Optical properties
Fluorescence

ASJC Scopus subject areas

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

Cite this

Solvent-templated folding of perylene bisimide macrocycles into coiled double-string ropes with solvent-sensitive optical signatures. / Spenst, Peter; Young, Ryan M.; Phelan, Brian T.; Keller, Michel; Dostal, Jakub; Brixner, Tobias; Wasielewski, Michael R; Wurthner, Frank.

In: Journal of the American Chemical Society, Vol. 139, No. 5, 08.02.2017, p. 2014-2021.

Research output: Contribution to journalArticle

Spenst, Peter ; Young, Ryan M. ; Phelan, Brian T. ; Keller, Michel ; Dostal, Jakub ; Brixner, Tobias ; Wasielewski, Michael R ; Wurthner, Frank. / Solvent-templated folding of perylene bisimide macrocycles into coiled double-string ropes with solvent-sensitive optical signatures. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 5. pp. 2014-2021.
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