Abstract
In this work we describe the approaches for the synthesis of lanthanide-containing homo- and heteronuclear complexes using 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-bis[(N-meso-(p-aminophenyl)-meso-triphenylporphyrincarbonyl)methoxy]-calix[4]arene (1). Such spatially preorganizedcalix[4]arene macrocycle facilitates lanthanide cation coordination, impacting the structure and analytical signal of porphyrin substituents. The study employs two synthesis strategies resulting in mononuclear and homobinuclear complexes, influenced by steric effects and changes in hydrogen bonding. The complexes exhibit changes in fluorescence spectra due to intramolecular dimerization and hydrogen bonding during complex formation. Mononuclear complexes (Ln-1) are synthesized under mild conditions, while homobinuclear complexes (Ln2-1) require high-boiling solvents and specific reaction conditions, detailed synthesis procedures are described. The structural changes during complex formation were analyzed with the use of NMR analysis. The absorption spectra of lanthanide complexes demonstrate shifts in maxima, reflecting coordination changes, with notable variations between mononuclear and homobinuclear complexes. Additionally, heteronuclear compounds with copper(II), zinc(II), and palladium(II) exhibit distinctive absorption patterns, emphasizing the role of d-metal ions. Luminescence studies reveal the sensitization of 4f-luminescence by both calix[4]arene and porphyrin fragments. The use of deuterated solvents enhances 4f-luminescence intensity, highlighting solvent effects. Furthermore, 4f-luminescence characteristics were investigated in both solid and solution states for heterometallic compounds, emphasizing differences between copper-containing and zinc/palladium-containing complexes. The results offer valuable insights into the design, synthesis, and spectral properties of these complexes, showcasing their potential applications in various fields, and the findings contribute to the understanding of lanthanide-porphyrin systems and their coordination behavior.
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