SYNTHESIS AND RESEARCH OF LANTHANIDE-CONTAINING HYBRID MATERIALS BASED ON POLYHEDRAL OLIGOMERIC SILSESQUIOXANES
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Keywords

: complexes, hybrid structure, luminescence materials, emission, nanosystems.

How to Cite

Ivakha, N., Berezhnytska, O., Trunova , E., & Rohovtsov, O. (2020). SYNTHESIS AND RESEARCH OF LANTHANIDE-CONTAINING HYBRID MATERIALS BASED ON POLYHEDRAL OLIGOMERIC SILSESQUIOXANES. Ukrainian Chemistry Journal, 86(6), 74-86. https://doi.org/10.33609/2708-129X.86.6.2020.74-86

Abstract

New hybrid materials were synthesized based on meteacroacetophenate neodymium (III) and erbium (III) and polyhedral oligomeric sissesquioxane POSS formula C24H72Cl8N8O12Si8. A warehouse has been put in place for a new synthesis. In the IR spectra of the synthesized hybrid materials in the range of 400–650 cm–1 there are oscillation bands that correspond to the valence oscillations of the bonds (Ln-O) and (Ln-N) and the deformation oscillations of the chelate ring. The decrease in intensity compared to the spectra of Ln(mphpd)3 complexes is due to the appearance of valence oscillations of the Ln-N bond and steric difficulties that arise when the complex coordinates to the sizable siloxane molecule. An additional intense broad band appears in the IR spectra, which is characterized by fluctuations in the valence of the Si-O-Si siloxane bond with a maximum of 1050 cm-1. The presence of a wide absorption band in the range of 1500–1700 cm-1, characterized by valence oscillations of ν (CO) and ν (CC), confirms the bidentate-cyclic coordination of β-diketonates. Thus, the shape and position of the bands in the IR spectra indicate the formation of a hybrid structure of the composition POSS- [Ln (mphpd)3]4. The shape, position, displacement and splitting of the spectral bands in the electronic spectra and diffuse reflectance spectra indicate the passage of the processes of complexation and the formation of complexes of non-cubic symmetry with coordination number 8. Thus, the presence of insignificant displacements of the absorption bands indicates the invariance of the coordination environment and the geometry of the coordination polyhedron for metal complexes and hydride systems based on them. The shift of the bands of supersensitive transitions in comparison with the spectra of metal complexes indicates both additional coordination of nitrogen atoms of the silsesquioxane molecule and some deformation of the coordination polyhedron, which is due to steric difficulties. According to the set of data from thermal and spectroscopic studies, the structure of the obtained hybrid material can be represented as follows. The results of EDX analysis, the method of dynamic light scattering and microphotographs are consistent and indicate the nanodispersity of the obtained systems.

 

https://doi.org/10.33609/2708-129X.86.6.2020.74-86
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