Kost S. Synthesis, structure and properties of lanthanide-containing complexes on the base of water-soluble calix[4]arenes.

The dissertation is devoted to establishment of correlation between the structure, composition and spectral-luminescent properties of the water-soluble phosphorus- and sulfur-containing calix[4]arenes and their new complexes with lanthanides. The received data forms the base of the first systematic study in the field of complex compounds of lanthanides with water-soluble functionalized calix[4]arenes and opens the possibility of their directional modification for the realization of effective 4f-luminescence. On the example of the first received complexes with phosphorus-containing calix[4]arenes it is shown that the coordination of lanthanide ion is determined by both the conditions of synthesis and structure of calix[4]arene. It is established that the change of phenolic to phosphorus-containing coordination center of water-soluble calix[4]arenes (-PO(C2H5)OH and -PO(OH)2 ) leads to the enhancement of the 4f-luminescence characteristics of lanthanide complexes (Tb (III), Dy (III), Yb (III), Nd (III)) with the increase of the covalent component of bond Ln-О. The largest values of the relative quantum yield and lifetime of 4f-luminescence were obtained for the terbium complexes with thiacalix[4]arenes. Heteronuclear f-d-complexes (f- Tb (III), Yb (III), d- Ni (II), Рd (II), Zn (II), Cd (II)) on the base of 5,11,17,23-tetrakis-(diethoxyphosphonyl)-25,26,27,28-tetrahydroxythiacalix[4]arene were synthesized at first time. It is identified that the intensity of 4f-luminescence in the f-d-complexes is conditioned by the relative position of the exited energy levels of both metals. The range of calix[4]arene compounds and their complexes with lutetium which exhibit the antibacterial activity were determined. Keywords: complex compounds, lanthanides, calix[4]arenes, thiacalix[4]arenes, spectral-luminescent properties.