Effect of an alkyl substituent and spacer length in benzene-centered tripodal diglycolamides on the sequestration of minor actinides

Seraj A. Ansari, Andrea Leoncini, Prasanta K. Mohapatra* (Corresponding Author), Jurriaan Huskens, Willem Verboom (Corresponding Author)

*Corresponding author for this work

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Abstract

Three benzene-centered tripodal diglycolamide (Bz-T-DGA) ligands, where diglycolamide (DGA) moieties are tethered to the central benzene ring through a methylene spacer and having either a hydrogen atom (LI) or an isopentyl group (LII) attached to the N-atom, and DGA moieties attached via an ethylene spacer and having an isopentyl group attached to the N-atom (LIII), were studied for their complexation and extraction abilities towards trivalent actinides and lanthanides. The distribution ratio of Am(iii) and Eu(iii) with 1 mmol L-1 ligand in 5% iso-decanol/n-dodecane followed the order: LII > LIII > LI. The substitution of the H atom with the isopentyl group on the N-atom of the DGA moieties resulted in two orders of magnitude enhancement in the extraction ability of the ligand. On the other hand, increase in the spacer length between the benzene ring and the DGA moieties resulted in several fold reduction in the extraction ability of the ligand. Spectroscopic studies with Eu3+ ions in acetonitrile also confirmed the metal/ligand complex formation constant in the order: LII > LIII > LI. Luminescence decay lifetimes of Eu3+/ligand complexes confirmed the absence of water molecules and that all the primary coordination sites of the metal ion are occupied by the ligands.

Original languageEnglish
Pages (from-to)13631-13640
Number of pages10
JournalDalton transactions
Volume47
Issue number38
DOIs
Publication statusPublished - 14 Oct 2018

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Actinoid Series Elements
Benzene
Ligands
Atoms
Lanthanoid Series Elements
Complexation
Metal ions
Luminescence
Hydrogen
Substitution reactions
Metals
Ions
Molecules
Water

Cite this

@article{f7f35b47f7ac42a798fdbda43e19ec5f,
title = "Effect of an alkyl substituent and spacer length in benzene-centered tripodal diglycolamides on the sequestration of minor actinides",
abstract = "Three benzene-centered tripodal diglycolamide (Bz-T-DGA) ligands, where diglycolamide (DGA) moieties are tethered to the central benzene ring through a methylene spacer and having either a hydrogen atom (LI) or an isopentyl group (LII) attached to the N-atom, and DGA moieties attached via an ethylene spacer and having an isopentyl group attached to the N-atom (LIII), were studied for their complexation and extraction abilities towards trivalent actinides and lanthanides. The distribution ratio of Am(iii) and Eu(iii) with 1 mmol L-1 ligand in 5{\%} iso-decanol/n-dodecane followed the order: LII > LIII > LI. The substitution of the H atom with the isopentyl group on the N-atom of the DGA moieties resulted in two orders of magnitude enhancement in the extraction ability of the ligand. On the other hand, increase in the spacer length between the benzene ring and the DGA moieties resulted in several fold reduction in the extraction ability of the ligand. Spectroscopic studies with Eu3+ ions in acetonitrile also confirmed the metal/ligand complex formation constant in the order: LII > LIII > LI. Luminescence decay lifetimes of Eu3+/ligand complexes confirmed the absence of water molecules and that all the primary coordination sites of the metal ion are occupied by the ligands.",
author = "Ansari, {Seraj A.} and Andrea Leoncini and Mohapatra, {Prasanta K.} and Jurriaan Huskens and Willem Verboom",
year = "2018",
month = "10",
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doi = "10.1039/c8dt02750a",
language = "English",
volume = "47",
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Effect of an alkyl substituent and spacer length in benzene-centered tripodal diglycolamides on the sequestration of minor actinides. / Ansari, Seraj A.; Leoncini, Andrea; Mohapatra, Prasanta K. (Corresponding Author); Huskens, Jurriaan; Verboom, Willem (Corresponding Author).

In: Dalton transactions, Vol. 47, No. 38, 14.10.2018, p. 13631-13640.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Effect of an alkyl substituent and spacer length in benzene-centered tripodal diglycolamides on the sequestration of minor actinides

AU - Ansari, Seraj A.

AU - Leoncini, Andrea

AU - Mohapatra, Prasanta K.

AU - Huskens, Jurriaan

AU - Verboom, Willem

PY - 2018/10/14

Y1 - 2018/10/14

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AB - Three benzene-centered tripodal diglycolamide (Bz-T-DGA) ligands, where diglycolamide (DGA) moieties are tethered to the central benzene ring through a methylene spacer and having either a hydrogen atom (LI) or an isopentyl group (LII) attached to the N-atom, and DGA moieties attached via an ethylene spacer and having an isopentyl group attached to the N-atom (LIII), were studied for their complexation and extraction abilities towards trivalent actinides and lanthanides. The distribution ratio of Am(iii) and Eu(iii) with 1 mmol L-1 ligand in 5% iso-decanol/n-dodecane followed the order: LII > LIII > LI. The substitution of the H atom with the isopentyl group on the N-atom of the DGA moieties resulted in two orders of magnitude enhancement in the extraction ability of the ligand. On the other hand, increase in the spacer length between the benzene ring and the DGA moieties resulted in several fold reduction in the extraction ability of the ligand. Spectroscopic studies with Eu3+ ions in acetonitrile also confirmed the metal/ligand complex formation constant in the order: LII > LIII > LI. Luminescence decay lifetimes of Eu3+/ligand complexes confirmed the absence of water molecules and that all the primary coordination sites of the metal ion are occupied by the ligands.

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