Interaction of Ln(3+) with Methyl-Substituted Cucurbit[n]urils (n=5,6) Derived from 3-Methyl Glycoluril

摘要

The interactions between a series of lanthanide cations (Ln(3+)) and methyl-substituted cucurbiturils (SPMeQ[5] and SHMeQ[6]) derived from a 3-methyl glycoluril have been investigated. Single-crystal X-ray diffraction analysis revealed that both SPMeQ[5] and SHMeQ[6] selectively interact with certain lanthanide ions. SPMeQ[5] forms coordination capsules in the presence of [CdCl4](2-). The Ln(3+) cations that interact are the four light lanthanides, La3+, Ce3+, Pr3+, and Nd3+, whereas the remaining lanthanide cations remain in solution. SHMeQ[6] formed adducts of SHMeQ[6] with aqua complexes of lanthanide cations ([Ln(H2O)(8)](3+)); for SHMeQ[6]-Ln(NO3)(3)-CdCl2-HCl systems (Ln=Gd-Lu), no solid crystals were obtained from systems that contained La, Ce, Pr, Nd, Sm, or Eu. Whereas solid crystals of adducts of SHMeQ[6] with aqua complexes of lanthanide cations (Ln=Sm-Lu) formed SHMeQ[6]-Ln(NO3)(3) systems in neutral solution, no solid crystals were obtained from systems that contained La, Ce, Pr, or Nd. These results suggest that SPMeQ[5]- and SHMeQ[6]-Ln(NO3)(3) systems could be useful for the selective isolation of these lighter or heavier lanthanide cations from mixtures. Energy-dispersive spectrometry indicated that the lighter or heavier lanthanide cations could be isolated from their heavier or lighter counterparts through interaction with SPMeQ[5] and SHMeQ[6].