title: Solvent-dependent aromatic versus antiaromatic conformational switching in meso-(heptakis)pentafluorophenyl [32]heptaphyrin.
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 1H 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 1H NMR spectra. Through our findings, we have demonstrated that the conformational switching dynamics between Hckel 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.
authors.affiliation: Spectroscopy Laboratory for Functional π-electronic Systems and Department of Chemistry, Yonsei University, Seodaemoon-gu, Seoul, Korea.
authors.forename: Min-Chul
authors.initials: MC
authors.lastname: Yoon
authors.forename: Jae-Yoon
authors.initials: JY
authors.lastname: Shin
authors.forename: Jong Min
authors.initials: JM
authors.lastname: Lim
authors.forename: Shohei
authors.initials: S
authors.lastname: Saito
authors.forename: Tomoki
authors.initials: T
authors.lastname: Yoneda
authors.forename: Atsuhiro
authors.initials: A
authors.lastname: Osuka
authors.forename: Dongho
authors.initials: D
authors.lastname: Kim