Bichromophoric hemicyanine dyes as fluorescence probes applied for monitoring of the photochemically initiated polymerization

Abstract

The spectroscopic properties of series homodimmeric hemicyanine dyes based on ( p-N,N-dimethylaminostyryl)benzothiazolium, ( p-N,N-dimethylaminostyryl)benzoxazolium, ( p-N,N-dimethylaminostyryl)-2,3,3-trimethyl-3H-indolium residues were determined. The absorption and fluorescence spectra of the dyes under study were measured in different polarity solvents at room temperature. On the basis of the solvatochromic behavior the ground state ( μ g ) and excited state ( μ e ) dipole moments of bis-(N,N-dimethylaminostyryl) derivatives were evaluated. The dipole moments ( μ g and μ e ) were estimated from solvatochromic shifts of absorption and fluorescence spectra as function of dielectric constant ( ε) and refractive index ( n) of applied solvents. The absorption and fluorescence spectra are only slightly affected by the solvent polarity. The analysis of solvatochromic behavior of the fluorescence spectra as a function of Δ f ( ε, n) revealed that the emission occurs from a high polarity excited state. The large dipole moment changes along with the red-shifted fluorescence, as the solvent polarity is increased, demonstrates the formation of an intramolecular charge transfer state (ICT). Six bichromophoric hemicyanine dyes, possessing benzothiazole, benzoxazole or indolinium group linked by 5 or 10 methylene groups were evaluated as fluorescence probes applied for monitoring of the polymerization process. The study on the changes in fluorescence intensity and spectroscopic shift of studied compounds were carried out during photochemically initiated polymerization of 2-ethyl-2-(hydroxymethyl)-propane-1,3-diol triacrylate (TMPTA).