Strapped calix[4]pyrrole as a lithium salts selective receptor through separated ion-pair binding

Hong, Kyeong Im; Kim, Hyeongcheol; Kim, Younghun; Choi, Moon Gun; Jang, Woo Dong

doi:10.1039/d0cc04809g

Cited by 22 publications

(22 citation statements)

References 20 publications

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“…Nevertheless, on account of its small size, high hydrophilicity, and small abundance ratio relative to other ubiquitous cations, the lithium cation is a particularly challenging target for selective recognition and extraction using ion pair receptors. [20][21][22][23][24][25] Numerous ion pair receptors reported thus far were designed to bind Na + , K + , and Cs + salts while Li + saltselective ion pair receptors are relatively rare. [10][11][12][13][14][15][16][17][18][19] The selectivity of an ion pair receptor for lithium salts highly depends on its cation binding site.…”

Section: Introductionmentioning

confidence: 99%

“…For instance, ion pair receptors functionalized with N-heterocyclic compounds such as phenanthroline, triazole, and pyridine as cation binding sites show a high selectivity for lithium salts. [20][21][22][23] Tripodal triamidophosphine oxide-based ion pair receptors were also reported to recognize lithium salt selectively in acetonitrile. [25] Taking this into consideration, we designed and synthesized tripodal ion pair receptor systems (1 and 2) by incorporating three nitrophenyl ureas and three amidonitroindoles as anion binding motifs into tris(pyridin-2-ylmethyl)amine, respectively (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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Tris(pyridin‐2‐ylmethyl)amine‐Based Ion Pair Receptors for Selective Lithium Salt Recognition

et al. 2022

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Tripodal ion pair receptors 1 and 2 consisting of tris(pyridine-2ylmethyl)amine as a cation binding site linked with nitrophenyl urea or amidonitroindole groups as anion binding motifs have been synthesized. 1 H NMR spectroscopic analyses carried out in 10 % DMSO in acetonitrile revealed that both ion pair receptors 1 and 2 are able to bind the LiCl ion pair with high selectivity over NaCl, KCl, RbCl, and CsCl. 1 H NMR spectroscopic analyses in combination with molecular mechanics calculations proved that the lithium cation is bound to the tris(pyridin-2-ylmethyl)amine subunit while the chloride anion interacts with the NHs of urea or amido indole groups via hydrogen bonds. The addition of fluoride to the lithium cation complexes of receptors 1 and 2 leads to the release of the lithium cation from the receptors whereas chloride and bromide are co-bound with lithium forming LiCl and LiBr ion pair complexes, respectively. The affinity of receptor 1 for the lithium cation was found to be improved by 5.0-fold when the counter anion of Cl À is cobound within the receptor.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Tris(pyridin‐2‐ylmethyl)amine‐Based Ion Pair Receptors for Selective Lithium Salt Recognition

et al. 2022

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“…Jang and co-workers synthesized a triazole-bearing strapped calix [4]pyrrole as a lithium selective ion-pair receptor. 32 This receptor proved effective at bringing lithium salts into an organic phase under LLE (CH 2 Cl 2 /water) conditions. In seminal early work, Smith and co-workers reported non-calix [4]pyrrole lithium ion-pair receptors.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Also reported was a phenanthroline-strapped calix[4]pyrrole that adsorbs LiCl under both model SLE (nitrobenzene) and LLE (CHCl 3 /water) conditions. Jang and co-workers synthesized a triazole-bearing strapped calix[4]pyrrole as a lithium selective ion-pair receptor . This receptor proved effective at bringing lithium salts into an organic phase under LLE (CH 2 Cl 2 /water) conditions.…”

Section: Introductionmentioning

confidence: 99%

Selective Separation of Lithium Chloride by Organogels Containing Strapped Calix[4]pyrroles

et al. 2021

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Reported herein are two functionalized crown ether strapped calix[4]pyrroles, H1 and H2. As inferred from competitive salt binding experiments carried out in nitrobenzene-d 5 and acetonitrile-d 3 , these hosts capture LiCl selectively over four other test salts, viz. NaCl, KCl, MgCl 2 , and CaCl 2 . Support for the selectivity came from density functional theory (DFT) calculations carried out in a solvent continuum. These theoretical analyses revealed a higher innate affinity for LiCl in the case of H1, but a greater selectivity relative to NaCl in the case of H2, recapitulating that observed experimentally. Receptors H1 and H2 were outfitted with methacrylate handles and subject to copolymerization with acrylate monomers and cross-linkers to yield gels, G1 and G2, respectively. These two gels were found to adsorb lithium chloride preferentially from an acetonitrile solution containing a mixture of LiCl, NaCl, KCl, MgCl 2 , and CaCl 2 and then release the lithium chloride in methanol. The gels could then be recycled for reuse in the selective adsorption of LiCl. As such, the present study highlights the use of solvent polarity switching to drive separations with potential applications in lithium purification and recycling.

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“…[14][15][16][17][18] However, reports of employing this strategy towards extracting lithium salts, in particular, remain scarce. [19][20][21][22][23] In general, heteroditopic receptor design typically relies on crown ether-based cation recognition sites and convergent hydrogen bond donor arrays as anion binding sites. 24,25 Over the last decade the emergence of sigma-hole interactions, such as halogen bonding (XB) and chalcogen bonding (ChB), have gained increasing attention in the field of anion recognition.…”

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confidence: 99%

Lithium halide ion-pair recognition with halogen bonding and chalcogen bonding heteroditopic macrocycles

et al. 2021

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Strapped calix[4]pyrrole as a lithium salts selective receptor through separated ion-pair binding

Abstract: Triazole-bearing strapped calix[4]pyrrole (1) was synthesized as a lithium salt selective ion pair receptor. 1H NMR spectral studies and X-ray crystallography showed that the capture of LiCl by 1 occurs...

Cited by 22 publications

References 20 publications

Tris(pyridin‐2‐ylmethyl)amine‐Based Ion Pair Receptors for Selective Lithium Salt Recognition

Tris(pyridin‐2‐ylmethyl)amine‐Based Ion Pair Receptors for Selective Lithium Salt Recognition

Selective Separation of Lithium Chloride by Organogels Containing Strapped Calix[4]pyrroles

Lithium halide ion-pair recognition with halogen bonding and chalcogen bonding heteroditopic macrocycles

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