title: Intramolecular exciplexes based on benzoxazole: photophysics and applications as fluorescent cation sensors.
abstract: Exciplex behaviour of three benzoxazole derivatives has been detected and intensively investigated by means of steady-state and time-resolved fluorescence techniques and transient absorption spectroscopy. The fluorescence of these compounds shows the properties which are typical for the excited state charge transfer complexes (exciplexes). Besides of the short wavelength fluorescence, which is similar in spectral distribution to the fluorescence of the electron acceptor (2-p-tolyl-benzoxazole), the red shifted, broad and structureless emission band is observed in solvents of low and medium polarity. The detailed analysis of the fluorescence data shows that the ratio of the CT and LE fluorescence initially increases with increasing solvent polarity, achieves a maximum, and drops for more polar solvents (epsilon(s) = 7). Similar behaviour is observed for the exciplex fluorescence lifetimes. The overall fluorescence and the relative intersystem crossing quantum yields show the decrease of these values with increasing solvent polarity. These observations have been explained on the basis of Marcus-type theory for nonradiative charge transfer rate constants. Increasing solvent polarity strongly accelerates the back electron transfer process which recovers the whole molecule in the ground state. The probability of the compact exciplex formation (i.e. sandwich-type structures) depends on solvent viscosity and degree of freedom of the bending of the saturated linker. The compound containing crown ether as a donor subunit may be used as a fluorescent indicator of inorganic cations (barium and lithium). We found an effective complexation of the compound in the ground state with barium and lithium cations. The complex is also stable in the excited state which manifests itself in strong increase of the fluorescence intensity.
authors.affiliation: Faculty of Chemistry, Jagiellonian University, 30-060 Krakow Ingardena 3, Poland.
authors.forename: Marek
authors.initials: M
authors.lastname: Mac
authors.forename: Tomasz
authors.initials: T
authors.lastname: Uchacz
authors.forename: Andrzej
authors.initials: A
authors.lastname: Danel
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Miranda
authors.forename: Cecilia
authors.initials: C
authors.lastname: Paris
authors.forename: Uwe
authors.initials: U
authors.lastname: Pischel