A method for the synthesis of reactive oligomeric silsesquioxanes, combining fragments of azo dye 4-(phenylazo)phenol and fluorescent dye Rhodamine B in various proportions in an organic shell was developed. These compounds were obtained by the reaction between the oligosilsesquioxane nanoparticles consisting of a mixture of linear, branched, ladder and polyhedral structures with epoxy groups in an organic frame (OSS–Ep) and the dyes. The structure of the synthesized substances was characterized by the methods of IR and 1H NMR spectroscopy.
The UV-Vis spectra of OSS–Pp–Rh in DMF solution contain absorption bands characteristic of both acidic (560 and 350 nm) and lactone (in the range of 318–326 nm) forms of Rhodamine B. The absorption band of 4-(phenylazo) phenol fragments corresponding to π−π* transition is observed at 348 nm and overlaps the absorption band of Rhodamine B at 350 nm.The intensity of the absorption bands of fragments of various dyes depends on their content in organic frame of the silsesquioxane core. The intensity of the absorption bands at 348 nm and at 560 nm increases with an increase in the content of 4-(phenylazo)phenol and Rhodamine B correspondingly.It should be noted that when using DMF as a solvent the absorption band corresponding to acidic form of Rhodamine B at 560 nm in the UV-Vis spectra of the compounds obtained is more intense than similar band in the spectrum of the original Rhodamine B. Therefore, the attachment of Rhodamine B to the silsesquioxane core of oligomeric silsesquioxanes mixture does not have a significant effect on the position of absorption maxima in the UV-spectrum and prevents dye’s fragments from converting to the colorless lactone form. In the fluorescence spectra of OSS–Pp–Rh obtained using DMF as a solvent a peak at λ max = 592 nm (λex= 520 nm) is observed. The position of the fluorescence peak and its intensity in the spectra at the same optical density of the medium practically do not depend on the ratio of fragments of 4-(phenylazo)phenol and Rhodamine B in organic frame of OSS–Pp–Rh. The combination of two different chromophores in organic shell of the silsesquioxane core broadens the range of absorbed light and the change of their ratio allows to adjust the absorption intensity in a certain area. The presence of hydroxyl groups makes it possible to introduce the obtained compounds into the composition of polymeric organic-inorganic nanocomposites by covalent bonding.
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