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- W2577029082 endingPage "2021" @default.
- W2577029082 startingPage "2014" @default.
- W2577029082 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, steady-state, 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." @default.
- W2577029082 created "2017-01-26" @default.
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- W2577029082 date "2017-01-27" @default.
- W2577029082 modified "2023-09-23" @default.
- W2577029082 title "Solvent-Templated Folding of Perylene Bisimide Macrocycles into Coiled Double-String Ropes with Solvent-Sensitive Optical Signatures" @default.
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- W2577029082 doi "https://doi.org/10.1021/jacs.6b11973" @default.
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