title: Ion-induced manipulation of photochemical pathways in crown ether compounds based on fluorinated oligophenylenevinylenes: the border between ultrafast photoswitches and photoproduced nanomaterials.
abstract: The photochemical and photophysical properties of the crown ethers trans,trans-1,4-bis[2-(3',4'-benzo 15-crown 5)ethenyl]-2,3,5,6-tetrafluorobenzene (1) and trans,trans-1,4-bis[2-(3',4'-benzo 18-crown 6) ethenyl]-2,3,5,6-tetrafluorobenzene (2) were investigated in the absence and presence of groups I and II metal ions. The photophysical methods used include steady state flurescence, uv spectroscopy, and ultrafast transient absorption spectroscopy. Both compounds showed solvatochromic behavior, due to intramolecular charge transfer state formation, and efficient fluorescence in polar solvents. Photophysical behavior was dependent on the metal ion. The addition of metal ions that completely fit into the crown ether cavity resulted in significant blue shifts in the fluorescence emission spectra (chemosensing properties). Partially fitting ions changed the fluorescence spectra slightly. Transient absorption measurements revealed fast and slow decay components with time constants of 10-20 and 500-600 ps for all fitting ions, respectively. The latter is assigned to a trans-cis photoisomerization process, which decreased in efficiency in the presence of partially fitting ions, i.e., increasing ion size. Steady state irradiation showed clear evidence of a change in the absorption spectra. Trans-cis photoisomerization and [2 + 2] photocycloaddition were found to compete with fluorescence. The ions Li+, Na+, and Ca2+, which fit into the cavity, direct the photoisomerization. Larger ions (K+, Rb+, Sr2+ and Ba2+) that partially fit the cavity cause photocycloaddition. Quantum yields of the photoreaction are between 0.1 and 0.3. Analysis of the photo-product obtained for the 1-Sr2+ system revealed a compound with a molecular weight of nanosize dimension, which was equivalent to seven mass units of 1. The higher molecular weight product was formed due to alternately stacked supramolecular assemblies.
authors.affiliation: Center for Photochemical Sciences, Department of Chemistry, Bowling Green State University, Bowling Green, Ohio 43403, USA.
authors.forename: B
authors.initials: B
authors.lastname: Strehmel
authors.forename: K B
authors.initials: KB
authors.lastname: Henbest
authors.forename: A M
authors.initials: AM
authors.lastname: Sarker
authors.forename: J H
authors.initials: JH
authors.lastname: Malpert
authors.forename: D Y
authors.initials: DY
authors.lastname: Chen
authors.forename: M A
authors.initials: MA
authors.lastname: Rodgers
authors.forename: D C
authors.initials: DC
authors.lastname: Neckers
mesh_terms: D003460:Crystallization / Q000379:methods*; D004988:Ethers, Cyclic / Q000138:chemical synthesis / Q000737:chemistry* / Q000528:radiation effects*; D005453:Fluorescence; D017611:Fluorine Compounds / Q000737:chemistry; D007477:Ions; D008027:Light; D046911:Macromolecular Substances; D009682:Magnetic Resonance Spectroscopy; D008670:Metals / Q000737:chemistry*; D008832:Microchemistry / Q000379:methods; D008846:Micromanipulation; D008958:Models, Molecular; D008970:Molecular Weight; D036103:Nanotechnology / Q000379:methods*; D055095:Optics and Photonics / Q000295:instrumentation; D010777:Photochemistry / Q000379:methods; D011108:Polymers / Q000737:chemistry; D013057:Spectrum Analysis / Q000379:methods
chemical_list: D004988:Ethers, Cyclic; D017611:Fluorine Compounds; D007477:Ions; D046911:Macromolecular Substances; D008670:Metals; D011108:Polymers