title: Tuning the excited-state dynamics of GFP-inspired imidazolone derivatives.
abstract: The excited-state dynamics of five derivatives of the GFP-chromophore, which differ by the position and nature of their substituents, has been investigated in solvents of various viscosity and polarity and in rigid media using femtosecond-resolved spectroscopy. In polar solvents of low viscosity, like acetonitrile or methanol, the fluorescence decays of all compounds are multiexponential, with average lifetimes of the order of a few picoseconds, whereas in rigid matrices (polymer films and low temperature glasses), they are single exponential with lifetimes of the order of a few nanoseconds and fluorescence quantum yields close to unity. Global analysis of the fluorescence decays recorded at several wavelengths and of the transient absorption spectra reveals the presence of several excited-state populations with slightly different fluorescence and absorption spectra and with distinct lifetimes. These populations are attributed to the existence of multiple ground-state conformers. From the analysis of the dependence of the excited-state dynamics on the solvent and on the nature of the substituents, it follows that the nonradiative deactivation of all these excited chromophores involves an intramolecular coordinate with large amplitude motion. However, depending on the solvent and substituent, additional channels, namely, inter- and intramolecular hydrogen bond assisted nonradiative deactivation, are operative. This allows tuning of the excited-state lifetime of the chromophore. Finally, an ultrafast photoinduced intramolecular charge transfer is observed in polar solvents with one derivative bearing a dimethylaminophenyl substituent.
authors.affiliation: Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Akad. G. Bontchev str. Bl. 9, Sofia 1113, Bulgaria. Irina.Petkova@unige.ch
authors.forename: Irina
authors.initials: I
authors.lastname: Petkova
authors.forename: Georgi
authors.initials: G
authors.lastname: Dobrikov
authors.forename: Natalie
authors.initials: N
authors.lastname: Banerji
authors.forename: Guillaume
authors.initials: G
authors.lastname: Duvanel
authors.forename: Robert
authors.initials: R
authors.lastname: Perez
authors.forename: Vladimir
authors.initials: V
authors.lastname: Dimitrov
authors.forename: Peter
authors.initials: P
authors.lastname: Nikolov
authors.forename: Eric
authors.initials: E
authors.lastname: Vauthey
mesh_terms: D003198:Computer Simulation; D049452:Green Fluorescent Proteins / Q000737:chemistry*; D007093:Imidazoles / Q000138:chemical synthesis / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D007093:Imidazoles; C117197:imidazolone; D049452:Green Fluorescent Proteins