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Effects of Si-Al Composition On the Fluorescence Spectra of 1-Naphthol During the Sol-Gel-Xerogel Transitions

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A systematic study has been carried out on the characteristic changes in the fluorescence spectra of 1-naphthol doped in the sol-gel-xerogel transition systems comprised of tetraethyl orthosilicate and diisobutoxyaluminium triethylsilicate catalyzed by a small amount of HCl, NH4OH, as well as under uncatalyzed conditions. In the systems containing large amounts of silicon, the fluorescence of 1-naphthol shifts to the red (a predominant emission from the 1La state) during the first stage of the reaction. This red shift indicates an increase in the polarity of the matrix surrounding 1-naphthol. In the second stage of the reaction, the spectrum shifts to the blue (a predominant emission from the 1Lb state), reflecting an increase in the micro-viscosity around 1-naphthol. In the systems containing relatively large amounts of aluminum, however, the spectrum just after mixing shows a larger red shift than that originating from the 1La emission. This large red-shifted fluorescence reflects the formation of a complex between 1-naphthol and the -O-Al-O-Si-O- network. The spectrum then shifted to the blue. The spectral behaviours observed indicate that there is a large and dynamic molecular-level change in the physicochemical properties of the matrix surrounding the 1-naphthol molecules during the sol-gel-xerogel transitions of the systems while the gelation phenomenon reflects macroscopic inflexibility although it is completely different from the restriction of movement at the molecular level.

Affiliations: 1: Department of Chemistry and Materials Engineering, Faculty of Engineering, Shinshu University, Wakasato, Nagano 380, Japan


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