Jagleniec Damian, Kopeć Aleksandra, Dobrzycki Łukasz, Romański Jan
Faculty of Chemistry, University of Warsaw, Pasteura 1, PL 02-093 Warsaw, Poland.
Inorg Chem. 2024 Dec 30;63(52):24797-24805. doi: 10.1021/acs.inorgchem.4c04127. Epub 2024 Dec 18.
A non-mulitmacrocyclic ion pair receptor with the ability to cooperatively bind lithium cations and halide anions is presented. These receptors feature a squaramide function for anion binding and are directly linked to a benzo-4-crown-12 unit to achieve selectivity toward lithium salts. Ion pair receptors and demonstrated stronger anion binding in the presence of cobound cations, while anion receptor lacks this property. X-ray measurements supported the simultaneous binding capability of ion pair receptors for both cations and anions. Under solid-liquid extraction (SLE) conditions in acetonitrile, ion pair receptors and selectively extract lithium salts. The more lipophilic receptor can extract LiCl in liquid-liquid extraction (LLE) and SLE, with the latter process notably more selective and effective. Improved LLE extraction of lithium chloride was achieved using copolymer containing receptor units in the structure. The inability of receptor or benzo-12-crown-4 ether to extract salts is attributed to the absence of a heteroditopic binding domain in their structures. This underscores the significant influence of both anion and cation binding domains in the receptor structures on the effective and selective extraction of lithium halide salts. The selectivity of these receptors and the polymeric material toward lithium salts suggests significant potential for extracting lithium from brine solutions with elevated halide content.
本文介绍了一种具有协同结合锂阳离子和卤化物阴离子能力的非多大环离子对受体。这些受体具有用于阴离子结合的方酰胺功能,并直接连接到苯并 - 4 - 冠 - 12单元以实现对锂盐的选择性。离子对受体 和 在共结合阳离子存在下表现出更强的阴离子结合能力,而阴离子受体 则缺乏此特性。X射线测量结果支持离子对受体对阳离子和阴离子的同时结合能力。在乙腈中的固液萃取(SLE)条件下,离子对受体 和 选择性地萃取锂盐。亲脂性更强的受体 可以在液液萃取(LLE)和SLE中萃取LiCl,后一过程的选择性和效率明显更高。使用结构中含有受体单元的共聚物 实现了氯化锂在LLE中的萃取效果改善。受体 或苯并 - 12 - 冠 - 4醚无法萃取盐类归因于其结构中不存在异双位点结合域。这突出了受体结构中的阴离子和阳离子结合域对卤化锂盐的有效和选择性萃取的重大影响。这些受体和聚合物材料对锂盐的选择性表明,从卤化物含量较高的卤水溶液中萃取锂具有巨大潜力。