Lanthanide Ion Interaction with a Crown Ether Methacrylic Polymer, Poly(1,4,7,10-tetraoxacyclododecan-2-ylmethyl methacrylate), as Seen by Spectroscopic, Calorimetric, and Theoretical Studies

The interaction between trivalent lanthanide ions and the polymer poly(1,4,7,10-tetraoxacyclododecan-2-ylmethyl methacrylate) (PCR4) containing pendant 1,4,7,10-tetraoxacyclododecane (12-crown-4) groups has been studied by various spectroscopic techniques, calorimetry and theoretical calculations. Evidence for the binding of Eu(III), Tb(III), and Ce(III) ions and PCR4 in solution was obtained by the lanthanide-induced 1H and 13C NMR shifts and the decay of Tb(III) luminescence. From the isotope effect observed on the decay of luminescence of Tb(III) bound to PCR4 in H2O and D2O solutions, it is suggested that complexation leads to a decrease in the number of water molecules from 8 or 9 to 7. In the solid state, studies by differential scanning calorimetry (DSC) show that the interaction between Ce(III), Tb(III), and Li(I) ions and PCR4 leads to an increase in the glass transition temperature (Tg) of the polymer. Electron paramagnetic resonance (EPR) spectra of Gd(III) in the presence of the polymer are qu...