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 language | English |
|---|---|
| Pages (from-to) | 2014-2021 |
| Number of pages | 8 |
| Journal | Journal of the American Chemical Society |
| Volume | 139 |
| Issue number | 5 |
| DOIs | |
| Publication status | Published - Feb 8 2017 |
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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 journal › Article
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TY - JOUR
T1 - Solvent-templated folding of perylene bisimide macrocycles into coiled double-string ropes with solvent-sensitive optical signatures
AU - Spenst, Peter
AU - Young, Ryan M.
AU - Phelan, Brian T.
AU - Keller, Michel
AU - Dostal, Jakub
AU - Brixner, Tobias
AU - Wasielewski, Michael R
AU - Wurthner, Frank
PY - 2017/2/8
Y1 - 2017/2/8
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.6b11973
DO - 10.1021/jacs.6b11973
M3 - Article
AN - SCOPUS:85012008922
VL - 139
SP - 2014
EP - 2021
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 5
ER -