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• W2094859078 endingPage "6715" @default.
• W2094859078 startingPage "6707" @default.
• W2094859078 abstract "Abstract We have investigated conformational switching dynamics of meso ‐heptakis(pentafluorophenyl) [32]heptaphyrin(1.1.1.1.1.1.1) in various solvents using steady‐state, time‐resolved, and temperature‐dependent spectroscopy. Absorption and fluorescence spectra of [32]heptaphyrin are quite sensitive to solvent environments. In nonpolar toluene, the antiaromatic figure‐of‐eight conformation is dominant, as seen in the X‐ray crystallography, based on broad and weak absorption bands without any fluorescence and moderate paratropic ring current. On the other hand, a well‐resolved sharp absorption spectrum, strong fluorescence, and diatropic ring current in the 1 H NMR spectrum in slightly polar THF indicate that most of [32]heptaphyrin molecules take significantly distorted Möbius conformation with aromatic character. By using transient absorption (TA) spectroscopy, the lowest singlet excited‐state lifetimes have been revealed to decay biexponentially with the time constants of 5 and 65 ps for figure‐of‐eight and Möbius conformations, respectively. Based on these results along with vertical excitation energy calculations, we are able to assign two conformers as Hückel antiaromatic and Möbius aromatic species, respectively; it shoulf be noted that the aromaticity/antiaromaticity does not change with temperature variation. Interestingly, in moderately polar solvent, ethyl ether, we find out that these two conformational isomers coexist with a dynamic equilibrium, as revealed by excitation‐wavelength‐dependent TA, temperature‐dependent absorption and 1 H NMR spectra. Through our findings, we have demonstrated that the conformational switching dynamics between Hückel antiaromatic and Möbius aromatic conformers in [32]heptaphyrin(1.1.1.1.1.1.1) are strongly affected by solvent medium as well as temperature." @default.
• W2094859078 created "2016-06-24" @default.
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• W2094859078 date "2011-05-12" @default.
• W2094859078 modified "2023-10-18" @default.
• W2094859078 title "Solvent-Dependent Aromatic versus Antiaromatic Conformational Switching in meso-(Heptakis)pentafluorophenyl [32]Heptaphyrin" @default.
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• W2094859078 doi "https://doi.org/10.1002/chem.201003736" @default.
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