Remarkable Enhancement in Extraction of Trivalent f-Block Elements Using a Macrocyclic Ligand with Four Diglycolamide Arms: Synthesis, Extraction, and Spectroscopic and Density Functional Theory Studies

Arunasis Bhattacharyya, Richard J.M. Egberink, Prasanta K. Mohapatra*, Parveen K. Verma, Avinash S. Kanekar, Ashok K. Yadav, Sambhu Nath Jha, Dibyendu Bhatacharyya, Jurriaan Huskens, Willem Verboom*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

1 Citation (Scopus)

Abstract

A multiple diglycolamide (DGA)-containing ligand having four DGA arms tethered to a tetraaza-12-crown-4 ring, viz. 2,2′,2′′,2′′′-(((1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetrakis(2-oxoethane-2,1-diyl)) tetrakis (oxy)) tetrakis(N,N-dioctylacetamide) (T12C4ODGA), was synthesized and evaluated for the extraction of different actinide and lanthanide ions, viz. Am3+, Eu3+, Pu4+, Np4+, and UO2 2+. The extraction efficiency of the present ligand was found to be the highest reported so far, more specifically for the trivalent metal ions Am3+ and Eu3+, when one considers the very low ligand concentration used in the present study, compared to that of the various previously reported multiple DGA-based ligands. The nature of the complexes formed during the extraction of Eu3+ was investigated using time-resolved fluorescence (TRFS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Both the solvent extraction and TRFS studies indicated the presence of 1:1 and 1:2 complexes during the extraction of Am3+ and Eu3+ having three inner-sphere water molecules in the 1:1 complex. Density functional theoretical (DFT) studies were performed on the Am3+ and Eu3+ complexes of both T12C4ODGA and an analogous compound having methyl groups in place of the n-octyl groups, and the DFT results of the T12C4ODGA nicely explain the extraction behavior of Am3+ and Eu3+.

Original languageEnglish
Pages (from-to)14885-14899
Number of pages15
JournalInorganic chemistry
Volume58
Issue number21
DOIs
Publication statusPublished - 4 Nov 2019

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Density functional theory
density functional theory
Ligands
ligands
augmentation
synthesis
Fluorescence
methyl compounds
Actinoid Series Elements
Extended X ray absorption fine structure spectroscopy
trivalent ions
Lanthanoid Series Elements
fluorescence
solvent extraction
Solvent extraction
Metal ions
metal ions
fine structure
Ions
Molecules

Keywords

  • UT-Hybrid-D

Cite this

Bhattacharyya, Arunasis ; Egberink, Richard J.M. ; Mohapatra, Prasanta K. ; Verma, Parveen K. ; Kanekar, Avinash S. ; Yadav, Ashok K. ; Jha, Sambhu Nath ; Bhatacharyya, Dibyendu ; Huskens, Jurriaan ; Verboom, Willem. / Remarkable Enhancement in Extraction of Trivalent f-Block Elements Using a Macrocyclic Ligand with Four Diglycolamide Arms : Synthesis, Extraction, and Spectroscopic and Density Functional Theory Studies. In: Inorganic chemistry. 2019 ; Vol. 58, No. 21. pp. 14885-14899.
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abstract = "A multiple diglycolamide (DGA)-containing ligand having four DGA arms tethered to a tetraaza-12-crown-4 ring, viz. 2,2′,2′′,2′′′-(((1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetrakis(2-oxoethane-2,1-diyl)) tetrakis (oxy)) tetrakis(N,N-dioctylacetamide) (T12C4ODGA), was synthesized and evaluated for the extraction of different actinide and lanthanide ions, viz. Am3+, Eu3+, Pu4+, Np4+, and UO2 2+. The extraction efficiency of the present ligand was found to be the highest reported so far, more specifically for the trivalent metal ions Am3+ and Eu3+, when one considers the very low ligand concentration used in the present study, compared to that of the various previously reported multiple DGA-based ligands. The nature of the complexes formed during the extraction of Eu3+ was investigated using time-resolved fluorescence (TRFS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Both the solvent extraction and TRFS studies indicated the presence of 1:1 and 1:2 complexes during the extraction of Am3+ and Eu3+ having three inner-sphere water molecules in the 1:1 complex. Density functional theoretical (DFT) studies were performed on the Am3+ and Eu3+ complexes of both T12C4ODGA and an analogous compound having methyl groups in place of the n-octyl groups, and the DFT results of the T12C4ODGA nicely explain the extraction behavior of Am3+ and Eu3+.",
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Remarkable Enhancement in Extraction of Trivalent f-Block Elements Using a Macrocyclic Ligand with Four Diglycolamide Arms : Synthesis, Extraction, and Spectroscopic and Density Functional Theory Studies. / Bhattacharyya, Arunasis; Egberink, Richard J.M.; Mohapatra, Prasanta K.; Verma, Parveen K.; Kanekar, Avinash S.; Yadav, Ashok K.; Jha, Sambhu Nath; Bhatacharyya, Dibyendu; Huskens, Jurriaan; Verboom, Willem.

In: Inorganic chemistry, Vol. 58, No. 21, 04.11.2019, p. 14885-14899.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Remarkable Enhancement in Extraction of Trivalent f-Block Elements Using a Macrocyclic Ligand with Four Diglycolamide Arms

T2 - Synthesis, Extraction, and Spectroscopic and Density Functional Theory Studies

AU - Bhattacharyya, Arunasis

AU - Egberink, Richard J.M.

AU - Mohapatra, Prasanta K.

AU - Verma, Parveen K.

AU - Kanekar, Avinash S.

AU - Yadav, Ashok K.

AU - Jha, Sambhu Nath

AU - Bhatacharyya, Dibyendu

AU - Huskens, Jurriaan

AU - Verboom, Willem

N1 - ACS deal

PY - 2019/11/4

Y1 - 2019/11/4

N2 - A multiple diglycolamide (DGA)-containing ligand having four DGA arms tethered to a tetraaza-12-crown-4 ring, viz. 2,2′,2′′,2′′′-(((1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetrakis(2-oxoethane-2,1-diyl)) tetrakis (oxy)) tetrakis(N,N-dioctylacetamide) (T12C4ODGA), was synthesized and evaluated for the extraction of different actinide and lanthanide ions, viz. Am3+, Eu3+, Pu4+, Np4+, and UO2 2+. The extraction efficiency of the present ligand was found to be the highest reported so far, more specifically for the trivalent metal ions Am3+ and Eu3+, when one considers the very low ligand concentration used in the present study, compared to that of the various previously reported multiple DGA-based ligands. The nature of the complexes formed during the extraction of Eu3+ was investigated using time-resolved fluorescence (TRFS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Both the solvent extraction and TRFS studies indicated the presence of 1:1 and 1:2 complexes during the extraction of Am3+ and Eu3+ having three inner-sphere water molecules in the 1:1 complex. Density functional theoretical (DFT) studies were performed on the Am3+ and Eu3+ complexes of both T12C4ODGA and an analogous compound having methyl groups in place of the n-octyl groups, and the DFT results of the T12C4ODGA nicely explain the extraction behavior of Am3+ and Eu3+.

AB - A multiple diglycolamide (DGA)-containing ligand having four DGA arms tethered to a tetraaza-12-crown-4 ring, viz. 2,2′,2′′,2′′′-(((1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetrakis(2-oxoethane-2,1-diyl)) tetrakis (oxy)) tetrakis(N,N-dioctylacetamide) (T12C4ODGA), was synthesized and evaluated for the extraction of different actinide and lanthanide ions, viz. Am3+, Eu3+, Pu4+, Np4+, and UO2 2+. The extraction efficiency of the present ligand was found to be the highest reported so far, more specifically for the trivalent metal ions Am3+ and Eu3+, when one considers the very low ligand concentration used in the present study, compared to that of the various previously reported multiple DGA-based ligands. The nature of the complexes formed during the extraction of Eu3+ was investigated using time-resolved fluorescence (TRFS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Both the solvent extraction and TRFS studies indicated the presence of 1:1 and 1:2 complexes during the extraction of Am3+ and Eu3+ having three inner-sphere water molecules in the 1:1 complex. Density functional theoretical (DFT) studies were performed on the Am3+ and Eu3+ complexes of both T12C4ODGA and an analogous compound having methyl groups in place of the n-octyl groups, and the DFT results of the T12C4ODGA nicely explain the extraction behavior of Am3+ and Eu3+.

KW - UT-Hybrid-D

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U2 - 10.1021/acs.inorgchem.9b02605

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