Fluorescence characteristics and photostability of benzoxazole derived donor-acceptor dyes in constrained media

The spectroscopic properties and photoreactivity of 2-(4-dimethylaminostryl)benzoxazole and its butadienyl analogue (abbreviated as DMASBO and BODB, respectively) were investigated in thin films of PS, PMMA and PVA polymer matrices as well as immobilized on silica surface. The experimental results showed that the investigated benzoxazole derivatives are sensitive to the polarity of its microenvironment even in the glassy matrices and in the solid state. The micropolarity of PVA and silica surface is greater than that of PMMA and PS. The combined results of fluorescence quantum yield and photoisomerization indicated that the size of the free volume within the polymer matrix influence strongly the photochemical reactivity of the used dyes. In PVA, which offers the smaller free volume, the photoreaction is totally blocked while the fluorescence yield is extremely enhanced relative to those in solutions and other polymer matrices. This is associated with an emission of green laser from DMASBO-PVA doped film when pumped by nitrogen laser (337 nm). The results showed that the present dyes are excellent probes for non-fluorescent systems presenting constrained geometry. The spectra of amorphous solid thin films of both dyes were also measured and show large red shifts relative to those in solutions indicating symmetric aggregation of molecules in the solid crystals.