A supramolecular lanthanide separation approach based on multivalent cooperative enhancement of metal ion selectivity.

A supramolecular lanthanide separation approach based on multivalent cooperative enhancement of metal ion selectivity.
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基于多价协同增强金属离子选择性的超分子稀土分离方法

DOI:
10.1038/s41467-018-02940-7
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发表时间:
2018-02-07
影响因子:
16.6
通讯作者:
Sun QF
Sun QF
中科院分区:
综合性期刊1区
文献类型:
--
作者:
Li XZ;Zhou LP;Yan LL;Dong YM;Bai ZL;Sun XQ;Diwu J;Wang S;Bünzli JC;Sun QF

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多价协同效应在超分子自组装过程中起着重要的作用。在这里,我们报道了由三齿配体(L1)与跨越元素周期表的各种金属离子自组装而成的金属有机M4L4四面体笼子的结构完整性和金属离子选择性的显著提高,包括碱土(CaII)、过渡金属(CdII)和所有稀土(LnIII)金属离子。所有这些M4L14笼对过量的金属离子和配体都是稳定的,这与具有与L1相同的配位基序的三齿(L2)配体和双三齿(L3)配体形成了鲜明的对比。此外,在四面体M4L4笼的混合金属自组装过程中观察到了高精度的金属离子自分类,而在M2L3笼上观察到了高精度的金属离子自分类。基于M4L4笼具有很强的协同金属离子自识别行为,提出了一种分离稀土元素的超分子方法,为设计新一代高效分离稀土的萃取剂提供了新的设计思路。
Multivalent cooperativity plays an important role in the supramolecular self-assembly process. Herein, we report a remarkable cooperative enhancement of both structural integrity and metal ion selectivity on metal-organic M4L4tetrahedral cages self-assembled from a tris-tridentate ligand (L1) with a variety of metal ions spanning across the periodic table, including alkaline earth (CaII), transition (CdII), and all the lanthanide (LnIII) metal ions. All these M4L14cages are stable to excess metal ions and ligands, which is in sharp contrast with the tridentate (L2) ligand and bis-tridentate (L3) ligand bearing the same coordination motif as L1. Moreover, high-precision metal ion self-sorting is observed during the mixed-metal self-assembly of tetrahedral M4L4cages, but not on the M2L3counterparts. Based on the strong cooperative metal ion self-recognition behavior of M4L4cages, a supramolecular approach to lanthanide separation is demonstrated, offering a new design principle of next-generation extractants for highly efficient lanthanide separation.
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