Two amphiphilic water-soluble sulfonatomethylated calix[4]resorcinarene derivatives were studied by various 1 H NMR techniques ( 1 H NMR titration, 2D NOESY, NMR diffusion measurements). The derivative with methyl moieties at the lower rim (1) was found to be nonaggregated in the range 0 -10 mM in aqueous solutions. Lengthening of the lower rim substituent to pentyl (2) results in self-aggregation of 2 in aqueous solutions with the aggregation number varying from 3 at 1 mM to 20 at 10 mM. The 2D NOESY 1 H NMR spectroscopy data reveal an unusual head-to-tail packing mode in aqueous solutions, resulting from the cooperative effect of weak hydrophobic interactions. Binding of guests (tetramethylammonium and N-methylpyridinium) results in additional stabilization of the aggregates whilst the head-to-tail packing mode of the aggregate is retained.
The thermal sensitivity enhancement of Tb3+-centered luminescence of dimer complexes with thiacalix[4]arene derivatives was achieved through their upper-rim bromination.
The work presents the synthesis of a novel calix[4]resorcinarene cavitand bearing four 1,3-diketone groups at the upper rim and its complex formation with Tb(III) ions in DMF and DMSO solutions. Electrospray ionization mass spectra, 1 H NMR, UV-Vis and luminescence spectra indicate a long (three hours at least) equilibration time for the complex formation between the cavitand and Tb(III) in alkaline DMF and DMSO solutions. These results are explained by the restricted keto-enol conversion, resulting from the steric hindrance effect of the methylenedioxy-groups linking the benzene rings within the cavitand framework.A facile synthetic route to convert luminescent Tb(III) complexes of various stoichiometries into luminescent hydrophilic colloids is disclosed in this work. The route is based on the reprecipitation of the Tb(III) complexes from DMF to aqueous solutions with further polyelectrolyte deposition without prior separation of the luminescent complexes. The luminescent colloids exhibit high stability over time and in buffer systems, which is a prerequisite for their applicability in analysis and biolabeling.
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