Trefoil-Shaped Outer-Sphere Ion Clusters Mediate Lanthanide(III) Ion Transport with Diglycolamide Ligands
Trefoil-Shaped Outer-Sphere Ion Clusters Mediate Lanthanide(III) Ion Transport with Diglycolamide Ligands
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DOI：
10.1021/jacs.7b07318
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发表时间：
2017-12-06
影响因子：
15
通讯作者：
Ellis, Ross J.
中科院分区：
文献类型：
--
作者：
Brigham, Derek M.;Ivanov, Alexander S.;Ellis, Ross J.
外层离子簇在许多重要的自然和技术过程中被推断出来，但它们的组装机制和溶液结构很难定义。在这里，我们表征了在用二甘醇酰胺配体进行液-液萃取过程中形成的烃溶液中形成的三叶形外球镧系元素氯化物和硝酸根离子簇。它们通过空间力和静电力组装，其中阴离子驻留在配位二甘醇酰胺配体之间的等距“裂缝”中，其位置满足排斥离子和吸引离子相互作用。我们的研究表明空间定向静电相互作用如何在有机溶液中组装稳定的外球离子簇，阐明控制离子簇组装和提取的新策略。
Outer-sphere ion clusters are inferred in many important natural and technological processes, but their mechanisms of assembly and solution structures are difficult to define. Here, we characterize trefoil-shaped outer-sphere lanthanide chloride and nitrate ion clusters in hydrocarbon solutions formed during liquid - liquid extraction with diglycolamide ligands. These are assembled through steric and electrostatic forces, where the anions reside in equidistant "clefts" between coordinating diglycolamide ligands in positions that satisfy both repulsive and attractive ion ion interactions. Our study shows how sterically directed electrostatic interactions may assemble stable outer-sphere ion clusters in organic solutions, elucidating new strategies for controlling ion cluster assembly and extraction.