N,N′-Dialkyl-N,N′-diaryl-1,10-phenanthroline-2,9-dicarboxamides as donor ligands for separation of rare earth elements with a high and unusual selectivity. DFT computational and experimental studies

Ustynyuk, Yu. A.; Borisova, Nataliya E.; Бабаин, В. А.; Gloriozov, I. P.; Manuilov, A. Y.; Kalmykov, Stepan N.; Alyapyshev, M. Yu.; Ткаченко, Л. И.; Kenf, E.; Ustynyuk, Nikolai A.

doi:10.1039/c5cc01620g

Cited by 59 publications

(55 citation statements)

References 34 publications

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“…23 Such trend limits possibility of Am separation from HLW because its separation from light lanthanides is going to be unsatisfactory. However, very different trends were observed for TBuPhen and Et(pEtPh)Phen.…”

Section: Extraction Of F-elements (Am and Lanthanides)mentioning

confidence: 99%

“…14 Diamides of 1,10-phenanthroline-2,9-dicarboxilyc acid were recently proposed as selective extractants for americium and curium. 22 Recently, it was shown 23 that the extraction ability of N,N'diethyl-N,N'-di(para-hexyl-phenyl)-1,10-phenantholine-4,7dichloro-2,9-dicarboxamide to lanthanides decreases from La to Lu. 18 The extraction of actinides 19,20 and some fission products 21 by 0.01 M solution of N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10phenanthroline (Et-Tol-DAPhen) in cyclohexanone was studied and SF Am/Eu being 67 was observed.…”

Section: Introductionmentioning

confidence: 99%

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1,10-Phenanthroline-2,9-dicarboxamides as ligands for separation and sensing of hazardous metals

et al. 2016

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1,10-phenanthroline-2,9-dicarboxamides of various structure were synthesized and studied as ligands for separation and sensing of d-and f-metals. It was found that the extraction ability of dialkyl-diaryl-diamide to lanthanides decreases from La to Lu and extraction of Am is close to light lanthanides (La-Pr). Tetraalkyl-diamide are not selective to lanthanides, instead exhibiting moderate selectivity in Am/Ln separation. The diamide complexes with lanthanides and d-elements were synthesized and characterized by XRD analysis. All diamides have demonstrated good extraction ability to environmentally hazardous metals (cadmium, lead, copper). The synthesized compounds were also tested as ionophores in PVC-plasticized potentiometric sensor membranes. Such sensors displayed no perceptible response to lanthanides but exhibited high sensitivity towards copper, zinc, cadmium and lead. These compositions can be considered as promising cross-sensitive sensors for multisensor systems.

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Section: Extraction Of F-elements (Am and Lanthanides)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

1,10-Phenanthroline-2,9-dicarboxamides as ligands for separation and sensing of hazardous metals

et al. 2016

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“…Only a handful of neutral ligands that exhibit high selectivity for light lanthanides in solvent extraction systems have been previously described . The majority of the known ligands exhibit the reverse trend, that is, by being more selective towards heavy lanthanides.…”

Section: Introductionmentioning

confidence: 99%

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

Healy

Ivanov

Karslyan

et al. 2019

Chemistry A European J

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Due to the ever‐increasing demand for high‐purity individual rare‐earth elements, novel and highly selective separation processes are increasingly sought after. Herein, we report a separation protocol that employs shape‐persistent 2,9‐bis‐lactam‐1,10‐phenanthroline (BLPhen) ligands exhibiting unparalleled selectivity for light trivalent lanthanides. The highly preorganised binding pockets of the ligands allowed for the separation of lanthanides with high fidelity, even in the presence of competing transition metals, in a biphasic separation system. Notably, the selectivity trends of the BLPhen ligands towards metal ions across the lanthanide series can be chemically modulated by altering the molecular rigidity of the extractant.

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“…According to the theoretical analysis,,, the covalent component of the metal‐ligand coordination bond makes the major contribution to the binding selectivity. Electron density transfer from the HOMO of the ligand to the vacant orbitals of the metal ion causes it.…”

Section: Introductionmentioning

confidence: 99%

Predictive Models for HOMO and LUMO Energies of N‐Donor Heterocycles as Ligands for Lanthanides Separation

Solov'ev

Ustynyuk

Zhokhova

et al. 2018

Molecular Informatics

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Quantum chemical calculations combined with QSPR methodology reveal challenging perspectives for the solution of a number of fundamental and applied problems. In this work, we performed the PM7 and DFT calculations and QSPR modeling of HOMO and LUMO energies for polydentate N-heterocyclic ligands promising for the extraction separation of lanthanides because these values are related to the ligands selectivity in the respect to the target cations. Data for QSPR modeling comprised the PM7 calculated HOMO and LUMO energies of N-donor heterocycles, including several types of both known and virtual undescribed polydentate ligands. Ensemble modeling included various molecular fragments as descriptors and different variable selection techniques to build consensus models (CMs) on a training set of 388 ligands using external cross-validation. CMs were then verified to make predictions for two external test sets: 45 ligands (T1) that were similar to the ligands of the training set, and 1546 structures (T2), which were substantially different from the ligands of the training set. The consensus models predict well in 5-fold cross-validation (RMSE =0.097 eV, RMSE =0.064 eV), and on the external test sets (T1: RMSE =0.26 eV, RMSE =0.24 eV; T2: RMSE =0.26 eV, RMSE =0.17 eV). An analysis of the results reveals that substituents in heteroaromatic rings of the ligands and at the amide nitrogens can deeply influence their metal binding properties.

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N,N′-Dialkyl-N,N′-diaryl-1,10-phenanthroline-2,9-dicarboxamides as donor ligands for separation of rare earth elements with a high and unusual selectivity. DFT computational and experimental studies

Cited by 59 publications

References 34 publications

1,10-Phenanthroline-2,9-dicarboxamides as ligands for separation and sensing of hazardous metals

1,10-Phenanthroline-2,9-dicarboxamides as ligands for separation and sensing of hazardous metals

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

Predictive Models for HOMO and LUMO Energies of N‐Donor Heterocycles as Ligands for Lanthanides Separation

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