2-Methylpyrrolidine derived 1,10-phenanthroline-2,9-diamides: promising extractants for Am(<scp>iii</scp>)/Ln(<scp>iii</scp>) separation

Lemport, Pavel S.; Evsiunina, Mariia V.; Matveev, Petr I.; Петров, В. А.; Pozdeev, Anton S.; Khult, E. K.; Nelyubina, Yu. V.; Isakovskaya, K. L.; Roznyatovsky, Vitaly A.; Gloriozov, I. P.; Tarasevich, B. N.; Aldoshin, Alexander S.; Петров, В. Г.; Kalmykov, Stepan N.; Ustynyuk, Yu. A.; Nenajdenko, Valentine G.

doi:10.1039/d2qi00803c

Cited by 23 publications

(31 citation statements)

References 48 publications

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“…As depicted in Figure 3 , even at 13 mM concentration, 5 shows limited affinity for light Lns, which is attributed to the larger reorganization energy required to complex with Ln in contrast to a preorganized ligand 1 . Consistently with other reports on 1,10-phenanthroline-2,9-diamides, 64 , 65 5 shows preference for light Lns. This is likely due to the rigid core and preorganization of two N donors.…”

Section: Results and Discussionsupporting

confidence: 92%

Size Selective Ligand Tug of War Strategy to Separate Rare Earth Elements

Johnson

Driscoll

Damron

et al. 2023

JACS Au

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Separating rare earth elements is a daunting task due to their similar properties. We report a “tug of war” strategy that employs a lipophilic and hydrophilic ligand with contrasting selectivity, resulting in a magnified separation of target rare earth elements. Specifically, a novel water-soluble bis-lactam-1,10-phenanthroline with an affinity for light lanthanides is coupled with oil-soluble diglycolamide that selectively binds heavy lanthanides. This two-ligand strategy yields a quantitative separation of the lightest (e.g., La–Nd) and heaviest (e.g., Ho–Lu) lanthanides, enabling efficient separation of neighboring lanthanides in-between (e.g., Sm–Dy).

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Section: Results and Discussionsupporting

confidence: 92%

Size Selective Ligand Tug of War Strategy to Separate Rare Earth Elements

Johnson

Driscoll

Damron

et al. 2023

JACS Au

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“…The average bond lengths of La/Nd/Eu/Lu–O L (2.468(4)/2.4839(2)/2.398(3)/2.305(2) Å) are shorter than that of La/Nd/Eu/Lu–N L (2.764(4)/2.722(3)/2.684(4)/2.620(3) Å) probably because the basicity of the O-donor is more “harder” than that of N-donor. Similar results have also been found in the lanthanide complexes with other hybrid N- and O-donor ligands. ,− The average bond lengths of La/Nd/Eu/Lu–O L (2.468(4)/2.4839(2)/2.398(3)/2.305(2) Å) are also slightly shorter than that of La/Nd/Eu/Lu–O S (2.523(4)/2.481(2)/2.446(4)/2.345(3) Å), indicating that the binding strength of NTAamide(Et) with the corresponding lanthanides is stronger than that with MeOH solvent molecules. What is more, all of the average bond lengths in the four lanthanide complexes decrease gradually with the decrease of ionic radii of Ln 3+ , indicating that heavier lanthanides form stronger complexes due to the lanthanide contraction effect, , which coincides with the trend of the complexing strength obtained by spectroscopic titration.…”

Section: Resultssupporting

confidence: 77%

Complexation of a Nitrilotriacetate-Derived Triamide Ligand with Trivalent Lanthanides: A Thermodynamic and Crystallographic Study

Wang

Song

et al. 2023

Inorg. Chem.

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Non-heterocyclic N-donor nitrilotriacetate-derived triamide ligands are one of the most promising extractants for the selective extraction separation of trivalent actinides over lanthanides, but the thermodynamics and mechanism of the complexation of this kind of ligand with actinides and lanthanides are still not clear. In this work, the complexation behaviors of N,N,N′,N′,N″,N″-hexaethylnitrilotriacetamide (NTAamide(Et)) with four representative trivalent lanthanides (La 3+ , Nd 3+ , Eu 3+ , and Lu 3+ ) were systematically investigated by using 1 H nuclear magnetic resonance ( 1 H NMR), ultraviolet−visible (UV−vis) and fluorescence spectrophotometry, microcalorimetry, and single-crystal X-ray diffractometry. 1 H NMR spectroscopic titration of La 3+ and Lu 3+ indicates that two species of 1:2 and 1:1 metal−ligand complexes were formed in NO 3 − and ClO 4 − media. The stability constants of NTAamide(Et) with Nd 3+ and Eu 3+ obtained by UV−vis and fluorescence titration show that the complexing strength of NTAamide(Et) with Nd 3+ is lower than that with Eu 3+ in the same anionic medium, while that of the same lanthanide complex is higher in ClO 4 − medium than in NO 3 − medium. Meanwhile, the formation reactions for all metal−ligand complexes are driven by both enthalpy and entropy. The structures of lanthanide complexes in the single ClO 4 − and NO 3 − medium and the mixed one were determined to be [LnL 2 (MeOH)](ClO 4 ) 3 (Ln = La, Nd, Eu, and Lu), [LaL 2 (EtOH) 2 ][La(NO 3 ) 6 ], and [LaL 2 (NO 3 )](ClO 4 ) 2 , separately. The average bond lengths of lanthanide complexes decrease gradually with the decrease in ionic radii of Ln 3+ , indicating that heavier lanthanides form stronger complexes due to the lanthanide contraction effect, which coincides with the trend of the complexing strength obtained by spectroscopic titration. This work not only reveals the thermodynamics and mechanism of the complexation between NTAamide ligands and lanthanides but also obtains the periodic tendency of complexation between them, which may facilitate the separation of trivalent lanthanides from actinides.

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“…Crystallization is less feasible for recycling and relatively difficult to integrate with the currently available equipment in industry compared to the case for LLE. 26,29 For liquid-liquid extraction, the extractant can be readily recycled, and the process has been demonstrated to be effective at separating many species, such as toxic compounds, [30][31][32] heavy metal ions, [33][34][35] and anions. [36][37][38] Yet, LLE-based sulfate separation is still underdeveloped.…”

Section: Introductionmentioning

confidence: 99%

Recognition-guided sulfate extraction and transport using tripodal hexaurea receptors

Chen

Zhao

et al. 2022

Inorg. Chem. Front.

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2-Methylpyrrolidine derived 1,10-phenanthroline-2,9-diamides: promising extractants for Am(iii)/Ln(iii) separation

Abstract: In this work we report on new examples of phenanthrolindiamides containing asymmetric centers in amide substituents. The synthesized ligands are expected to have complex thermodynamic behavior. Their structure was unambiguously...

Cited by 23 publications

References 48 publications

Size Selective Ligand Tug of War Strategy to Separate Rare Earth Elements

Size Selective Ligand Tug of War Strategy to Separate Rare Earth Elements

Complexation of a Nitrilotriacetate-Derived Triamide Ligand with Trivalent Lanthanides: A Thermodynamic and Crystallographic Study

Recognition-guided sulfate extraction and transport using tripodal hexaurea receptors

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