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

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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
Issue number5
Publication statusPublished - Feb 8 2017


ASJC Scopus subject areas

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

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