Efficient Separation of Light Lanthanides(III) by Using Bis‐Lactam Phenanthroline Ligands

Healy, Mary R.; Ivanov, Alexander S.; Karslyan, Yana; Bryantsev, Vyacheslav S.; Moyer, Bruce A.; Jansone‐Popova, Santa

doi:10.1002/chem.201806443

Cited by 64 publications

(72 citation statements)

References 42 publications

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“…We observed an increased separation factor for the La:Dy mixture solely based on an increased EF solid value, which was EF solid =297±31. This is one of the highest single step enrichment factors known for RE separations . Therefore, this method could potentially be targeted for ultrapure Dy separations/purifications.…”

Section: Resultsmentioning

confidence: 99%

Magnetic Field Directed Rare‐Earth Separations

et al. 2019

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The separation of rare‐earth ions from one another is challenging due to their chemical and physical similarities. Nearly all rare‐earth separations rely upon small changes in ionic radii to direct speciation or reactivity. Herein, we show that the intrinsic magnetic properties of the rare‐earth ions impact the separations of light/heavy and selected heavy/heavy binary mixtures. Using TriNOx3− ([{(2‐tBuNO)C6H4CH2}3N]3−) rare‐earth complexes, we efficiently and selectively crystallized heavy rare earths (Tb–Yb) from a mixture with light rare earths (La and Nd) in the presence of an external Fe14Nd2B magnet, concomitant with the introduction of a concentration gradient (decrease in temperature). The optimal separation was observed for an equimolar mixture of La:Dy, which gave an enrichment factor of EFLa:Dy=297±31 for the solid fraction, compared to EFLa:Dy=159±22 in the absence of the field, and achieving a 99.7 % pure Dy sample in one step. These results indicate that the application of a magnetic field can improve performance in a molecular separation system for paramagnetic rare‐earth cations.

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Section: Resultsmentioning

confidence: 99%

Magnetic Field Directed Rare‐Earth Separations

et al. 2019

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“…This is one of the highest single step enrichment factors known for RE separations. [5,18] Therefore, this method could potentially be targeted for ultrapure Dy separations/purifications.M ixtures that contained La:Er-(TriNOx) also gave an extremely large solid enrichment factor of EF La:Er = 202 AE 22 and an overall separation factor of SF La:Er = 471 AE 71. After obtaining separation factors for all of the binary mixtures of La:HRE(TriNOx) complexes,arelationship was observed that generally indicated increasing SF La:HRE performance with the total angular momentum (J) for the free ion of the HRE 3+ cations (Figure 3).…”

Section: Resultsmentioning

confidence: 99%

Magnetic Field Directed Rare‐Earth Separations

et al. 2019

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The separation of rare-earth ions from one another is challenging due to their chemical and physical similarities. Nearly all rare-earth separations rely upon small changes in ionic radii to direct speciation or reactivity.H erein, we show that the intrinsic magnetic properties of the rare-earth ions impact the separations of light/heavy and selected heavy/heavy binary mixtures.U sing TriNOx 3À ([{(2-t BuNO)-C 6 H 4 CH 2 } 3 N] 3À )r are-earth complexes,w ee fficiently and selectively crystallized heavy rare earths (Tb-Yb) from amixture with light rare earths (La and Nd) in the presence of an external Fe 14 Nd 2 Bm agnet, concomitant with the introduction of ac oncentration gradient (decrease in temperature). The optimal separation was observed for an equimolar mixture of La:Dy,which gave an enrichment factor of EF La:Dy = 297 AE 31 for the solid fraction, compared to EF La:Dy = 159 AE 22 in the absence of the field, and achieving a99.7 %pure Dy sample in one step.T hese results indicate that the application of am agnetic field can improve performance in am olecular separation system for paramagnetic rare-earth cations.

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“…On the other hand, the "inverse sequence" is observed exclusively with structurally rigid materials. For example, Healy et al [20] developed a chelate ligand of the phenanthroline skeleton, wherein the sizecompatibility of ions to the binding space provided by the rigid ligand is more accommodating to the light lanthanide ions as compared to the heavy lanthanide ions.…”

Section: Introductionmentioning

confidence: 99%

Transmetalation in a Ce(III)‐phosphoester Crystalline Coordination Polymer with an Exceptionally High Selectivity for Yb(III) and Lu(III)

Tasaki-Handa

Tsuda

Shibukawa

et al. 2020

Chemistry An Asian Journal

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A novel crystalline coordination polymer containing Ce3+ and bis(4‐nitrophenyl) phosphate (L), CeL3, was synthesized and its unique transmetalation selectivities toward Yb3+ and Lu3+ in the lanthanide series were evaluated. The relatively large difference in transmetalation selectivity between the neighboring Tm3+ and Yb3+ species is noteworthy because the reactivities of heavy lanthanides are generally considerably similar. The structural strain of the polymeric framework is likely responsible for this unusual trend. Powder X‐ray diffraction analysis indicated that, in the cases of only Yb3+ and Lu3+, large differences in their ionic sizes compared to that of Ce3+ in the parent framework may induce a structural strain after solid solution formation, while cleavage of the relatively weak Ce−O bond allows the formation of new Yb−O and Lu−O bonds with the incoming Yb3+ and Lu3+, respectively. Structural phase transitions likely caused by the heterogeneous nucleation of the Yb‐ (or Lu‐) type phase were also observed.

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Efficient Separation of Light Lanthanides(III) by Using Bis‐Lactam Phenanthroline Ligands

Cited by 64 publications

References 42 publications

Magnetic Field Directed Rare‐Earth Separations

Magnetic Field Directed Rare‐Earth Separations

Magnetic Field Directed Rare‐Earth Separations

Transmetalation in a Ce(III)‐phosphoester Crystalline Coordination Polymer with an Exceptionally High Selectivity for Yb(III) and Lu(III)

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