Stilbene-Like Molecules as Fluorescent Probes Applied for Monitoring of Polymerization Process

Abstract

2-(p-N,N-dimethylaminostyryl)benzoxazole (OS), 2-(p-N,N-dimethylaminostyryl)-benzothiazole (SS) and 2-(p-N,N-dimethylaminostyryl)naphtiazole (PS) were prepared and their absorption and fluorescence spectra were measured in various solvents at room temperature. On the basis of the solvatochromic behavior the ground state (mu(g)) and excited state (mu(e)) dipole moments of these pN,N-dimethylaminostyryl derivatives were evaluated. The dipole moments (mu(g) and mu(e)) were estimated from solvatochromic shifts of absorption and fluorescence spectra as function of the dielectric constant (epsilon) and refractive index (n) of applied solvents. The absorption spectra only slightly are affected by the solvent polarity in contrast to the fluorescence spectra that are highly solvatochromic and display a large Stokes shift. The analysis of the solvatochromic behavior of the fluorescence spectra as function of Deltaf (epsilon, n) revealed that the emission occurs from a high polarity excited state. The large dipole moment change along with the strongly red-shifted fluorescence, as the solvent polarity is increased, demonstrate the formation of an intramolecular charge transfer state (ICT). Compounds under the study were used as fluorescence probes for monitoring the kinetics of polymerization. The study on the changes in fluorescence intensity and spectroscopic shifts of studied compounds were carried out during thermally initiated polymerization of methyl methacrylate (MMA) and during photoinitiated polymerization of 2-ethyl-2-(hydroxymethyl)propane-1,3-diol triacrylate (TMPTA).