Lithium is recognized as being significantly important due to its various applications in different areas especially in energy technology. In the present study, self-assembled nanostructured liquid-crystalline (LC) materials, that selectively bind lithium cations, have been developed for the first time. Wedge-shaped crown ether derivatives bearing dibenzo-14-crown-4 (DB14C4) or 12-crown-4 moieties are able to act as LC lithium-selective receptors. We have found that complexation of these receptors with lithium perchlorate induces liquid-crystalline columnar phases, while sodium perchlorate is immiscible with both receptors. Remarkably, a receptor consisting of DB14C4 as an effective lithium-selective ligand exhibits high selectivity for LiCl over NaCl, KCl, RbCl and CsCl. The lithium selectivity was demonstrated and investigated by 1H NMR, 1H COSY and FT-IR spectroscopic measurements. The preferred coordination number of four and the ideal cavity geometry of the DB14C4 moiety of the receptor are shown to be key factors for the high lithium selectivity. This new design of LC lithium-selective receptors opens unexplored paths for the development of methods to fabricate nanostructured materials for efficient selective lithium recognition.
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机译：由于锂在不同领域的各种应用，特别是在能源技术中，锂被认为是非常重要的。在本研究中，首次开发了选择性结合锂阳离子的自组装纳米结构液晶（LC）材料。带有二苯并-14-冠-4（DB14C4）或12-冠-4部分的楔形冠醚衍生物能够充当LC锂选择性受体。我们已经发现，这些受体与高氯酸锂的络合会诱导液晶柱状相，而高氯酸钠与两种受体都不能混溶。值得注意的是，由DB14C4作为有效的锂选择性配体组成的受体对LiCl具有比NaCl，KCl，RbCl和CsCl更高的选择性。通过 1 1 H NMR， 1 H COZY和FT-IR光谱法证明和研究了锂的选择性。受体的DB14C4部分的优选配位数为4和理想的腔几何结构是实现高锂选择性的关键因素。 LC锂选择性受体的这一新设计为开发用于高效选择性锂识别的纳米结构材料的方法开发开辟了未探索的道路。
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