Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide‐Extraction Properties and Metal Ion Speciation in Bis‐1,2,4‐Triazine Ligands
作者:Andrey V. Zaytsev、Rachel Bulmer、Valery N. Kozhevnikov、Mark Sims、Giuseppe Modolo、Andreas Wilden、Paul G. Waddell、Andreas Geist、Petra J. Panak、Patrik Wessling、Frank W. Lewis
DOI:10.1002/chem.201903685
日期:2020.1.7
the two classes of ligand, with a lower percentage of the extracted 1:2 complexes being formed for ligands 8 and 10. The structures of the solid state 1:1 and 1:2 complexes formed by 8 and 10 with YIII, LuIII and PrIII are very similar to those formed by 2 and 3 with LnIII. Ligand 10 forms CmIII and EuIII 1:2 complexes that are thermodynamically less stable than those formed by ligand 3, suggesting that
报道了三种新的含有五元脂肪族环的新型bis-1,2,4-triazine配体的合成和评估。相比,更疏水性配体1 - 3的含六元脂族环,相关的分配比率˚F -嵌段金属离子为大小在每种情况下低大约一个数量级。配体10显示出从硝酸中有效,选择性和快速地分离出Am III和Cm III。使用NMR滴定和竞争实验,时间分辨激光荧光光谱和X射线晶体学探测了具有三价f嵌段金属离子的配体的形态。而四齿配体8和10形成的Ln III配合物与它们的疏水性更高的类似物2和3具有相同的化学计量,在两类配体之间观察到形态上的显着差异,而针对配体8和10形成的提取的1:2配合物的百分比更低。10。8和10与Y III,Lu III和Pr III形成的固态1:1和1:2配合物的结构与2和3与Ln III形成的固态配合物的结构非常相似。配体10形成的Cm III和Eu III 1:2配合物在热力学上不如配体3形成的配合物