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

Xiao-Zhen Li, Li-Peng Zhou, Liang-Liang Yan, Ya-Min Dong, Zhuan-Ling Bai, Xiao-Qi Sun, Juan Diwu, Shuao Wang, Jean-Claude Bünzli () and Qing-Fu Sun ()
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Xiao-Zhen Li: Chinese Academy of Sciences
Li-Peng Zhou: Chinese Academy of Sciences
Liang-Liang Yan: Chinese Academy of Sciences
Ya-Min Dong: Chinese Academy of Sciences
Zhuan-Ling Bai: Soochow University
Xiao-Qi Sun: Chinese Academy of Sciences
Juan Diwu: Soochow University
Shuao Wang: Soochow University
Jean-Claude Bünzli: Swiss Federal Institute of Technology
Qing-Fu Sun: Chinese Academy of Sciences

Nature Communications, 2018, vol. 9, issue 1, 1-10

Abstract: Abstract 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 M4L4 tetrahedral 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 M4L14 cages 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 M4L4 cages, but not on the M2L3 counterparts. Based on the strong cooperative metal ion self-recognition behavior of M4L4 cages, a supramolecular approach to lanthanide separation is demonstrated, offering a new design principle of next-generation extractants for highly efficient lanthanide separation.

Date: 2018
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DOI: 10.1038/s41467-018-02940-7

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