title: Tuning photoinduced intramolecular electron transfer by electron accepting and donating substituents in oxazolones.
abstract: The solvatochromic and spectral properties of oxazolone derivatives in various solvents were reported. Fluorescence spectra clearly showed positive and negative solvatochromism depending on substituents. The solvatochromic plots and quantum chemical computations at DFT-B3LYP/6-31 + G(d,p) level were used to assess dipole moment changes between the ground and the first excited singlet-states. The electron accepting nitro substituent at the para-position increased the π-electron mobility, however, the 3,5-dinitro substituent decreased the π-electron mobility as a result of inverse accumulation of the electronic density as compared with that of its ground state. Experimental and computational studies proved that the photoinduced intramolecular electron transfer (PIET) is responsible for the observed solvatochromic effects. We demonstrate that PIET can be finely tailored by the position of the electron accepting and donating substituents in the phenyl ring of the oxazolone derivatives. We propose that the photoactive CPO derivatives are new molecular class of conjugated push-pull structures using azlactone moiety as the π-conjugated linker and may find applications in photovoltaic cells and light emitting diodes.
authors.affiliation: Department of Chemistry, Dokuz Eylül University, 35160, Izmir, Turkey.
authors.forename: Gülsiye
authors.initials: G
authors.lastname: Oztürk
authors.forename: Hasan
authors.initials: H
authors.lastname: Karabıyık
authors.forename: Muhittin
authors.initials: M
authors.lastname: Aygün
authors.forename: Serap
authors.initials: S
authors.lastname: Alp
authors.forename: Serdar
authors.initials: S
authors.lastname: Ozçelik
mesh_terms: D004579:Electron Transport; D008958:Models, Molecular; D008968:Molecular Conformation; D010081:Oxazolone / Q000737:chemistry*; D055668:Photochemical Processes; D013050:Spectrometry, Fluorescence
chemical_list: D010081:Oxazolone