First Example of Fluorinated Phenanthroline Diamides: Synthesis, Structural Study, and Complexation with Lanthanoids

Avagyan, Nane A.; Lemport, Pavel S.; Лысенко, К. А.; Gudovannyy, Alexey O.; Roznyatovsky, Vitaly A.; Петров, В. А.; Vokuev, M. F.; Ustynyuk, Yuri A.; Nenajdenko, Valentine G.

doi:10.3390/molecules27154705

Cited by 11 publications

(19 citation statements)

References 50 publications

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“…Synthesis and Structure of Alkyl Aryl Diamides of Phenanthroline. Studied ligands were prepared by reacting 4,7-dichloro-1,10-phenanthroline-2,9-dicarboxylic acid chloride with the corresponding amines according to a procedure similar to that described earlier for their synthesis 3,26,31 The ligand L1 crystallized with the MeCN solvent molecule due to the formation of an intermolecular C−H•••N hydrogen bond with the nitrogen atom of the phenanthroline ring with a distance of 2.6 Å (Figure 2).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…209−211°C. 1 N 2 ,N 9 -Bis(4-butylphenyl)-4,7-dichloro-N 2 ,N 9 -diethyl-1,10-phenanthroline-2,9-dicarboxamide 31…”

Section: ■ Conclusionmentioning

confidence: 99%

“…Determination of Uranium Capacity. Solvent extraction tests for a series of 4,7-dichloro-N 2 ,N 9diethyl-N 2 ,N 9 -bis(4-alkylphenyl)-1,10-phenanthroline-2,9-dicarboxamides 31 (L1−L4) was performed in 1.5 mL polypropylene tubes. The volumes of aqueous and organic phases were 0.5 mL each.…”

Section: (L3)mentioning

confidence: 99%

“…In order to reduce the Brønsted basicity of the synthesized ligands and to increase their solubility in extraction tests, chlorine atoms were incorporated into the phenanthroline core. These chlorine atoms can be further replaced using cross-coupling reactions catalyzed by palladium salts or with F atoms for purposes of fine-tuning . We performed here a study of such uranium complexes both in solution and in solid states using different physicochemical methods.…”

Section: Introductionmentioning

confidence: 99%

“…These chlorine atoms can be further replaced using cross-coupling reactions catalyzed by palladium salts 30 or with F atoms for purposes of fine-tuning. 31 We performed here a study of such uranium complexes both in solution and in solid states using different physicochemical methods.…”

Section: ■ Introductionmentioning

confidence: 99%

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Solvation-Anionic Exchange Mechanism of Solvent Extraction: Enhanced U(VI) Uptake by Tetradentate Phenanthroline Ligands

et al. 2022

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Phenanthroline diamides (L) demonstrated a unique ability to extract uranium from nitric acid solutions into a polar organic solvent forming complexes of 1:2 stoichiometry as tight ion pairs {[UO2 LNO3]+[UO2(NO3)3]−} by a novel extraction mechanism, which is a combination of two already well-known mechanisms: solvation and ion-pair anion exchange. A UV–vis study was used to confirm the formation of such complexes directly in the organic phase. Moreover, chemical synthesis and single crystal growth were performed to confirm unambiguously the structure of the complexes in the solid state.

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Section: ■ Results and Discussionmentioning

confidence: 99%

“…209−211°C. 1 N 2 ,N 9 -Bis(4-butylphenyl)-4,7-dichloro-N 2 ,N 9 -diethyl-1,10-phenanthroline-2,9-dicarboxamide 31…”

Section: ■ Conclusionmentioning

confidence: 99%

Section: (L3)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Solvation-Anionic Exchange Mechanism of Solvent Extraction: Enhanced U(VI) Uptake by Tetradentate Phenanthroline Ligands

et al. 2022

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1,10-Phenanthroline-2,9-dicarboxylic acid diamides: synthesis, structure, and solubility

et al. 2023

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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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First Example of Fluorinated Phenanthroline Diamides: Synthesis, Structural Study, and Complexation with Lanthanoids

Cited by 11 publications

References 50 publications

Solvation-Anionic Exchange Mechanism of Solvent Extraction: Enhanced U(VI) Uptake by Tetradentate Phenanthroline Ligands

Solvation-Anionic Exchange Mechanism of Solvent Extraction: Enhanced U(VI) Uptake by Tetradentate Phenanthroline Ligands

1,10-Phenanthroline-2,9-dicarboxylic acid diamides: synthesis, structure, and solubility

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

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