The incorporation of upper vs lower rim substituted thia- and calix[4]arene ligands into polydiacethylene polymeric bilayers for rational design of sensors to heavy metal ions

1,3-Diketone calix [4]arene (CA) and thiacalix [4]arene (TCA), with the hydrophobic substituents introduced onto lower or upper rims respectively, form mixed aggregates with 10,12-pentacosadiynoic acid (PCDA) through the thin film hydration technique. Computer simulations, showing the arrangement of TCA and CA molecules in supramolecular clusters with PCDA molecules, suggest that PCDA assemblies with both cyclophanes are a convinient basis for the coordination of metal ions. However, photopolymerization of mixed aggregates reveals more disruption of the vesicular nanostructure of polydiacetylene (PDA) when CA molecules are included compared to TCA. The incorporation of the TCA and CA ligands influences the ability of the mixed PDA-bilayers to conformational and spectral changes and provides tight coordination of Tb3+ ions and efficient sensitizing of the Tb3+-centered luminescence. The PDA-bilayers incorporated by terbium TCA complex provide more sensitive response on the series of heavy metal ions vs their CA-based analogues. The surface exposed TCA rims and carboxylate moieties of PDA provide two different binding sites for Tb3+ and heavy metal ions. Both distribution of Tb3+ and heavy metal ions between these sites and heterometallic complex formation are revealed as the factors affecting the luminescence response of PDA-TCA terbium complex in the solutions of heavy metal ions. The interplay between these factors is the reason for the different luminescence response of PDA-TCA terbium complex on Cd2+, Hg2+ and Pb2+ ions. The PDA-vesicles incorporated by terbium TCA complex exhibit easier phase separation vs the PDA vesicles themselves, which favors the extraction of Pb2+ ions.