Rusakova N. Lanthanide-containing heteronuclear complexes based on functionalized calix[4]arenes and porphyrins: synthesis, structure and luminescent properties

The presented thesis is devoted to the synthesis of new lanthanide-containing heteronuclear complexes based on two classes of macrocyclic compounds - functionalized calix[4]arenes and porphyrins, and investigation of the influence of the nature of organic ligand and second metal on the spectral-luminescent properties of the systems. The synthesis of f-s- and f-d-heteronuclear complexes with calix[4]arenes and porphyrins different by the nature and position of substituent was carried out for the first time. It was found that depending on the nature of the ligand f- (in the case calix[4]arenes) or d-blocks (porphyrins) should be used to obtain a compound with the necessary luminescent properties. The X-ray analysis of single crystal of calix[4]arene showed that the formation of intramolecular hydrogen bonds stabilizes the molecule in "cone" conformation and thus creates preorganized coordination unit that is capable for effective binding of metal ions. The correlation between the intensity of 4f-luminescence of lanthanide-containing complexes of calix[4]arenes and a number of chromophore fragments, length of alkyl linker and nature of the d-metal was established for the first time. It was shown that d-metal ions can act as quencher or sensitizer of 4f-luminescence depending on the location of their energy levels. It was found that the composition and 4f-luminescence of f-s-heteronuclear complexes based on crown-calix[4]arenes are influenced by the nature of s-cation and crown ether and linker. It was shown that complexes of lanthanides with functionalized porphyrins can exhibit effective luminescence at the same time in visual and NIR region. Cu(II), Ni(II), Co(II) ions quench molecular and 4f-luminescence, while Zn(II) and Pd(II) ions increase the intensity depending on the nature of lanthanide, d-metal and presence of oxygen.