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
KW - 22/4 OA procedure
UR - http://www.scopus.com/inward/record.url?scp=85073462523&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.9b02605
DO - 10.1021/acs.inorgchem.9b02605
M3 - Article
C2 - 31609594
AN - SCOPUS:85073462523
SN - 0020-1669
VL - 58
SP - 14885
EP - 14899
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 21
ER -