Adducts of aqua complexes of Ln(3 ) with a dihydroxylated symmetrical octamethyl-substituted cucurbituril: potential applications for isolation of heavier lanthanides
Adducts of aqua complexes of Ln(3 ) with a dihydroxylated symmetrical octamethyl-substituted cucurbituril: potential applications for isolation of heavier lanthanides
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Ln(3) 与二羟基化对称八甲基取代的葫芦脲的水配合物的加合物：分离较重镧系元素的潜在应用
作者：
Shen Fang Fang;Chen Kai;Hua Zi Yi;Wang Yuan;Xu Jing;Chen Min Dong;Zhang Yun Qian;Tao Zhu
研究了一系列镧系离子（Ln3+）与对称二羟基化八甲基取代葫芦脲{(OH)2OMeQ[6]}的相互作用。单晶x射线衍射分析表明，在（OH）2OMeQ[6] -Ln (NO3)3 - H2O体系中，（OH）2OMeQ[6]与镧系阳离子（[Ln(H2O)8]3+）的水络合物形成加合物，Ln = Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu。然而，含有La， Ce, Pr， Nd和Sm的体系没有得到固体晶体。x射线衍射分析表明，固体加合物虽然属于两个同构基团，但（OH）2OMeQ[6]和[Ln(H2O)8]3+配合物之间的相互作用以及相应的超分子组合没有显著差异。等温滴定量热实验表明，（OH）2OMeQ[6]与[Ln(H2O)8]3+配合物相互作用的热力学参数对应于上述两个体系的两个周期，较轻的镧系离子倾向于留在溶液中，较重的镧系离子形成结晶固体。能量色散光谱（EDS）表明，omq[6]与镧系离子的相互作用可以提供一种将较重的镧系离子与较轻的镧系离子分离的方法。
The interaction of a series of lanthanide cations (Ln3+) with a di-hydroxylated symmetrical octamethyl-substituted cucurbituril {(OH)2OMeQ[6]} has been investigated. Single-crystal X-ray diffraction analysis has revealed that the interaction results in the formation of adducts of (OH)2OMeQ[6] with aqua complexes of lanthanide cations ([Ln(H2O)8]3+), Ln = Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu in (OH)2OMeQ[6]–Ln(NO3)3–H2O systems. However, no solid crystals were obtained from systems containing La, Ce, Pr, Nd and Sm. X-ray diffraction analysis has revealed that although the solid adducts fall into two isomorphous groups, there are no significant differences in the interactions between (OH)2OMeQ[6] and [Ln(H2O)8]3+ complexes and in the corresponding supramolecular assemblies. Thermodynamic parameters for the interaction between (OH)2OMeQ[6] and [Ln(H2O)8]3+ complexes based on isothermal titration calorimetry experiments show two periods corresponding to the above two systems, with the lighter lanthanide cations preferring to remain in solution and the heavier lanthanide cations forming crystalline solids. Energy dispersive spectroscopy (EDS) has shown that the interaction of OMeQ[6] with lanthanide cations could provide a means of isolating heavier lanthanide cations from their lighter counterparts.