Role of diluent in the unusual extraction of Am<sup>3+</sup> and Eu<sup>3+</sup> ions with benzene-centered tripodal diglycolamides: local structure studies using luminescence spectroscopy and XAS

Verma, Parveen K.; Mohapatra, Prasanta K.; Yadav, Ashok K.; Jha, S. N.; Bhattacharyya, D.; Leoncini, Andrea; Huskens, Jurriaan; Verboom, Willem

doi:10.1039/d1nj02594e

Cited by 3 publications

(1 citation statement)

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“…Identifying and characterizing solution structures can be done computationally through electronic structure computations and molecular dynamics simulations , and experimentally through X-ray absorption, NMR spectroscopy, and excitation/emission spectroscopy. − In particular, ab initio molecular dynamics (AIMD) simulations and extended X-ray absorption fine structure (EXAFS) spectroscopy have both been used to successfully characterize several solvated lanthanide and actinide structures. Most of the published research utilizing these techniques has centered on the structure of the ion within aqueous solutions, either as a dissolved salt − or bound to chelators useful for heavy-metal extraction and biomedical applications. − Despite the importance of nonaqueous solutions for several of the applications cited above, far fewer studies examine the ion coordination spheres of such ions in organic solutions beyond resolving the structures of liquid–liquid-extracted ion–ligand complexes. ,,− …”

Section: Introductionmentioning

confidence: 99%

Solution Structures of Europium Terpyridyl Complexes with Nitrate and Triflate Counterions in Acetonitrile

et al. 2023

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Lanthanide−ligand complexes are key components of technological applications, and their properties depend on their structures in the solution phase, which are challenging to resolve experimentally or computationally. The coordination structure of the Eu 3+ ion in different coordination environments in acetonitrile is examined using ab initio molecular dynamics (AIMD) simulations and extended X-ray absorption fine structure (EXAFS) spectroscopy. AIMD simulations are conducted for the solvated Eu 3+ ion in acetonitrile, both with or without a terpyridyl ligand, and in the presence of either triflate or nitrate counterions. EXAFS spectra are calculated directly from AIMD simulations and then compared to experimentally measured EXAFS spectra. In acetonitrile solution, both nitrate and triflate anions are shown to coordinate directly to the Eu 3+ ion forming either ten-or eight-coordinate solvent complexes where the counterions are binding as bidentate or monodentate structures, respectively. Coordination of a terpyridyl ligand to the Eu 3+ ion limits the available binding sites for the solvent and anions. In certain cases, the terpyridyl ligand excludes any solvent binding and limits the number of coordinated anions. The solution structure of the Eu-terpyridyl complex with nitrate counterions is shown to have a similar arrangement of Eu 3+ coordinating molecules as the crystal structure. This study illustrates how a combination of AIMD and EXAFS can be used to determine how ligands, solvent, and counterions coordinate with the lanthanide ions in solution.

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Section: Introductionmentioning

confidence: 99%

Solution Structures of Europium Terpyridyl Complexes with Nitrate and Triflate Counterions in Acetonitrile

et al. 2023

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Unique transport behaviour of Am(III)/Eu(III) ions across a supported liquid membrane containing a TREN-based diglycolamide dendrimer ligand

et al. 2022

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Appropriately functionalized dendrimers are exotic ligands and are expected to give rise to better extraction/transport results than the corresponding monofunctional ones. Diglycolamide- (DGA) based dendrimers and their transport studies are rarely reported. Transport of Am(III) and Eu(III) was studied across a PTFE- (polytetrafluoroethylene) based flat sheet supported liquid membrane containing a tris(2-aminoethyl)amine (TREN) dendrimer ligand containing six DGA pendent arms (termed as TREN-G1-DGA) in 5% isodecanol modified n-dodecane. The transport results were compared with those of the monofunctional ligand TODGA (N,N,N′,N′-tetra-n-octyl diglycolamide). In case of a 5.75 × 10−4 M TREN-G1-DGA solution, Am(III) transport was slower than that of Eu(III) under identical conditions. In case of TREN-G1-DGA the role of acid on the metal ion transport was less important than that while using TODGA as a carrier. However, a nitric acid medium is much more suitable for metal ion transport than a mixture containing sodium nitrate as the major component. Insight into the extraction and transport of the Eu(III) complexes was obtained from luminescence spectroscopic studies.

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Understanding the separation of trivalent lanthanides and actinides using multiple diglycolamide-containing ligands: a review

Bhattacharyya,

Mohapatra,

Verboom

2024

Radiochimica Acta

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The complexation and separation behaviour of trivalent actinides and lanthanides with various multiple diglycolamide (DGA) group-containing ligands are compiled in the present review. The DGA arms are anchored on various scaffolds, viz., C- and N-pivot tripodal backbones, benzene-centred tripodal backbones, calix[4]arene, pillar[5]arene and azamacrocycle scaffolds. Dendrimers of different generations having DGA arms were also evaluated for the extraction and complexation studies of trivalent actinide and lanthanide ions. The extraction efficiency of the DGA units increases significantly when they are grouped together on a single backbone/scaffold. Furthermore, the selectivity was found to improve in many cases, particularly with respect to the UO2 2+ ion. This is very important for the development of suitable ligands for the extraction/separation of the actinide and lanthanide ions. Combined experimental, luminescence and DFT studies on the complexation of trivalent actinides and lanthanides with these DGA-based ligands are quite useful to understand their extraction and separation behaviour and this review article gives a critical analysis of the results available in the literature.

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Role of diluent in the unusual extraction of Am³⁺ and Eu³⁺ ions with benzene-centered tripodal diglycolamides: local structure studies using luminescence spectroscopy and XAS

Abstract: Two benzene-centered tripodal diglycolamide ligands (LI and LII) were used for the extraction of Am3+ and Eu3+ from nitric acid solutions into a diluent medium of n-dodecane modified with varying...

Cited by 3 publications

References 51 publications

Solution Structures of Europium Terpyridyl Complexes with Nitrate and Triflate Counterions in Acetonitrile

Solution Structures of Europium Terpyridyl Complexes with Nitrate and Triflate Counterions in Acetonitrile

Unique transport behaviour of Am(III)/Eu(III) ions across a supported liquid membrane containing a TREN-based diglycolamide dendrimer ligand

Understanding the separation of trivalent lanthanides and actinides using multiple diglycolamide-containing ligands: a review

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Role of diluent in the unusual extraction of Am3+ and Eu3+ ions with benzene-centered tripodal diglycolamides: local structure studies using luminescence spectroscopy and XAS

Abstract: Two benzene-centered tripodal diglycolamide ligands (LI and LII) were used for the extraction of Am3+ and Eu3+ from nitric acid solutions into a diluent medium of n-dodecane modified with varying...

Cited by 3 publications

References 51 publications

Solution Structures of Europium Terpyridyl Complexes with Nitrate and Triflate Counterions in Acetonitrile

Solution Structures of Europium Terpyridyl Complexes with Nitrate and Triflate Counterions in Acetonitrile

Unique transport behaviour of Am(III)/Eu(III) ions across a supported liquid membrane containing a TREN-based diglycolamide dendrimer ligand

Understanding the separation of trivalent lanthanides and actinides using multiple diglycolamide-containing ligands: a review

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Role of diluent in the unusual extraction of Am³⁺ and Eu³⁺ ions with benzene-centered tripodal diglycolamides: local structure studies using luminescence spectroscopy and XAS