Modification of calix[4]arenes with CMPO-functions at the wide rim. Synthesis, solution behavior, and separation of actinides from lanthanides.
Modification of calix[4]arenes with CMPO-functions at the wide rim. Synthesis, solution behavior, and separation of actinides from lanthanides.
复制标题
在宽边缘处用 CMPO 官能团对杯[4]芳烃进行修饰。
DOI：
10.1039/b307929e
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发表时间：
2003
影响因子：
3.2
通讯作者：
J. Dozol
中科院分区：
文献类型：
--
作者：
C. Schmidt;M. Saadioui;V. Böhmer;Valéry Host;M. Spirlet;J. Desreux;F. Brisach;F. Arnaud;J. Dozol
首次合成了两个含四-N(Me)-CO-CH2-P(O)PH2残基的杯[4]芳烃四元醚(Y=C5H11，C14H29)。研究了它们从酸性水相到有机相(CH2Cl2，NPHE)的萃取能力。与相应的-NH-类似物相比，它们是效率较低的萃取剂，对重稀土的选择性不那么明显，而AM3+对Eu3+仍有有趣的选择性。还测定了部分稀土盐在均相(甲醇、乙腈)中的稳定常数，但没有考虑不同的萃取结果。对Gd~(3+)的络合也进行了弛豫度测量，结果表明N-甲基化合物有更强的聚集，而与NH类似物相比，1：1的络合物[L]/[Gd~(3+)]更小。动态光散射测量也支持聚集体的形成。戊基醚的单晶X射线结构表明，自由配体为C2对称的收缩锥形构象。
Two calix[4]arene tetraethers (Y = C5H11, C14H29) bearing on their wide rim four -N(Me)-CO-CH2-P(O)Ph2 residues were synthesized for the first time. Their ability to extract lanthanides and actinides from an acidic aqueous phase to organic phases (CH2Cl2, NPHE) was studied. In comparison to the corresponding -NH-analogs, they are less efficient extractants, the selectivity for the light over the heavy lanthanides is less pronounced, while there is still an interesting selectivity of Am3+ over Eu3+. Stability constants for selected lanthanide salts were determined also in homogenous phase (methanol, acetonitrile) but do not account for the different extraction results. The complexation of Gd3+ was also followed by relaxivity (NM RD) measurements, which suggest an even stronger aggregation for the N-methyl compound while the 1:1 complex is reached for a smaller ratio [L]/[Gd3+] compared to the NH analog. The formation of aggregates is also supported by dynamic light scattering measurements. A single crystal X-ray structure of the pentyl ether reveals a C2-symmetrical pinched cone conformation for the free ligand.