Semenishyn M. Homo- and heteronuclear lanthanide-containing complexes on the base of modified porphyrins: synthesis and properties

The thesis is devoted to the relationship between structure and spectral-luminescent properties of symmetrical meso-substituted alkyl- and arylporphyrins, as well as porphyrin modified by aminopolycarbonic acids and their homo- and heteronuclear complexes with lanthanides. Obtained data suggest that sensitization of 4f-luminescence of the porphyrin chromophore occurs despite the fact that the lanthanide ion is located on the periphery of the porphyrin. On the instance of meso- and beta-modified porphyrins shows that the higher efficiency of 4f-luminescence is observed for the complexes based on beta-substituted porphyrins. It was found that the nature of aminopolycarbonic acid influences on 4f-luminescence intensity due to different denticity of ligands. It was shown that increasing of the number of lanthanide ions on the periphery leads to increasing of luminescence quantum yield. It was determined that the d-metal ions have different effects on the emission of the complexes: paramagnetic ions (Cu2+, Co2+ and Ni2+), as a rule, quench the molecular fluorescence and the 4f-luminescence, and diamagnetic ions (Zn2+ and Pd2+) can reduce or increase the efficiency of 4f-luminescence depending on the nature of lanthanide, d-metal and the presence of oxygen, while the molecular fluorescence becomes less effective, and its spectrum is suffered a significant hypsochromic shift. It is noted that in contrast to the unmodified lanthanide-porphyrinates, the mononuclear and heteronuclear (with Zn2+ or Pd2+) complexes based on porphyrin modified aminopolycarbonic acids are able to show the emission properties in the characteristic range of free bases (650-720 nm), and in the near IR region (850-1350 nm), that is characteristic for Yb3+ and Nd3+ ions.