Healy Mary R, Ivanov Alexander S, Karslyan Yana, Bryantsev Vyacheslav S, Moyer Bruce A, Jansone-Popova Santa
Chemical Sciences Division, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37831-6119, USA.
Present address: Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, OR 97331-4003, USA.
Chemistry. 2019 May 2;25(25):6326-6331. doi: 10.1002/chem.201806443. Epub 2019 Mar 27.
Due to the ever-increasing demand for high-purity individual rare-earth elements, novel and highly selective separation processes are increasingly sought after. Herein, we report a separation protocol that employs shape-persistent 2,9-bis-lactam-1,10-phenanthroline (BLPhen) ligands exhibiting unparalleled selectivity for light trivalent lanthanides. The highly preorganised binding pockets of the ligands allowed for the separation of lanthanides with high fidelity, even in the presence of competing transition metals, in a biphasic separation system. Notably, the selectivity trends of the BLPhen ligands towards metal ions across the lanthanide series can be chemically modulated by altering the molecular rigidity of the extractant.
由于对高纯度单一稀土元素的需求不断增加,人们越来越追求新颖且具有高选择性的分离工艺。在此,我们报道了一种分离方案,该方案采用形状持久的2,9-双内酰胺-1,10-菲咯啉(BLPhen)配体,对轻三价镧系元素表现出无与伦比的选择性。这些配体高度预组织的结合口袋能够在双相分离体系中实现镧系元素的高保真分离,即使存在竞争性过渡金属也不受影响。值得注意的是,通过改变萃取剂的分子刚性,可以对BLPhen配体对整个镧系元素系列金属离子的选择性趋势进行化学调控。