Snurnikova O. Synthesis, structure and spectral-luminescent properties of polynuclear complexes of lanthanides with functionalized calix[4]arenes

The thesis is devoted to the synthesis and study of the structure, the spectral-luminescent properties of homo- and heteronuclear complexes of lantanides with p-tert-butylcalix[4]arenes modified by the lower rim with carboxyl-, benzimidazole- and porphyrin-containing substituents. The synthesized complexes were characterized by number of the physico-chemical methods of investigation: elemental analysis, mass spectrometry, IR-, NMR-, UV- and fluorescence (steady-state and kinetic) spectroscopy. In the complexes with the carboxymethoxycalix[4]arenes in series substituted 4f-luminescence of lanthanides in the visible (Eu(III), Tb(III)) and the IR region (Yb(III), Nd(III), Er(III)) of the spectrum is observed. The intensity of luminescence in complexes with asymmetric calix[4]arenes is higher than symmetrical ligands. The functionalization of the carboxyl groups by benzimidazole-containing substituents leads to an increase in 4f-luminescence only in the case of mono- and disubstituted compounds. On the example which has been shown that removal of the benzimidazole substituent at lengthening the alkyl linker leads to decrease of quantum yield of luminescence. In f-d-heteronuclear complexes of 1,3-dibenzimidazole substituted calix[4]arene with Zn(II) and Re(I) and calix[4]arene-diporphyrine with Zn(II) and Pd(II) 4f-luminescence of ytterbium are sensitized by d-metal ions. While in the calix[4]arene-porphyrine associates the nuture of d-metal does not affect the 4f-luminescence of Yb(III). It was found that dibenzimidazole derivatives of calix[4]arene and their homo- and heteronuclear complexes exhibit biological activity, which, along with spectral-luminescent characteristics, indicates the promise of their use in biological research. Keywords: symmetric and asymmetric substituted p-tert-calix[4]arenes, calix[4]arene-porphyrine conjugates, lanthanides, luminescence, heteronuclear complexes.