Oligomeric silsesquioxanes containing dye Rhodamine B in an organic shell

Abstract

A method for the synthesis of amphiphilic reactive oligomeric silsesquioxanes (OSS) with fragments of Rhodamine B fluorescent dye and hydroxyl groups in organic shell (OSS-Rh) by the reaction between carboxyl groups of the dye and epoxy groups of the mixture of oligomeric silsesquioxanes (OSS-Ep) was developed. The structure of the synthesized substance was characterized by the methods of IR and 1H NMR spectroscopy.
 The UV-spectrum of the OSS-Rh compound in dimethylformamide (DMF) solution was characterized by absorption bands of both the colored zwitterion (562 nm and 350 nm) and the colorless lactone (318 nm) forms of Rhodamine B. The absorption band at 562 nm in the spectrum of OSS-Rh in DMF solution was more intense than the analogous band in the spectrum of the original Rhodamine B. Therefore, the attachment of Rhodamine B to the silsesquioxane core of an oligomeric silsesquioxanes mixture does not have a significant effect on the position of the absorption maxima in UV-spectrum and prevents dye’s fragments from converting to the colorless lactone form.
 In the fluorescence spectra of both Rhodamine B and OSS-Rh, obtained using ethyl alcohol as a solvent, a peak is observed at λmax = 570 nm (λex = 500 nm). In the fluorescence spectrum of OSS-Rh obtained in DMF, a fluorescence peak is observed at λmax = 586 nm (λex = 520 nm). Consequently, the replacement of ethanol by DMF is accompanied by a bathochromic shift of the fluorescence peak of OSS-Rh. In the fluorescence spectrum of Rhodamine B at the same conditions, the peak of fluorescence is absent because of transition of the dye to the lactone form. The compounds obtained can be used in formation of functional Langmuir-Blodgett films as well as in obtaining polymer nanocomposites by covalent bonding.

Oligomeric Silsesquioxanes Combining Azo- And Fluorescent Dyes in Organic Shell

“…Ранее нами на основе OSS-Ep были получены соединения, в органическом обрамлении которых присутствует один из указанных красителей: 4-(фенилазо)фенол [19] либо Rhodamine B [20]. В данном исследовании разработан метод cочетания в органическом обрамлении силсесквиоксанового ядра двух различных типов красителей (OSS-Pp-Rh).…”

“…Исходный OSS-Ep был получен в соответствии с методиками [16,17]. Согласно данным MALDI ToF масс-спектрометрии [19,20], OSS-Ep является смесью силсесквиоксановых структур общей формулы [RSiO 1.5 ] n , среди которых линейные, лестничные, полностью и неполностью конденсированные соединения со степенью полимеризации п = 8-13.…”