A roadmap to uranium ionic liquids: Anti-crystal engineering

Yaprak, Damla; Spielberg, Eike T.; Bäcker, Tobias; Richter, Mark; Mallick, Bert; Klein, Axel; Mudring, Anja -Verena

doi:10.1002/chem.201303333

Title: A roadmap to uranium ionic liquids: Anti-crystal engineering

Journal Article · Tue Apr 15 00:00:00 EDT 2014 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201303333· OSTI ID:1240910

Yaprak, Damla ^[1]; Spielberg, Eike T. ^[1]; Bäcker, Tobias ^[1]; Richter, Mark ^[1]; Mallick, Bert ^[1]; Klein, Axel ^[2]; Mudring, Anja -Verena ^[3]

Ruhr-Univ. Bochum (Germany)
Univ. zu Koln, Koln (Germany)
Ruhr-Univ. Bochum (Germany); Ames Lab., Ames, IA (United States)

In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C₄mim) cation. As dithiocarbamate ligands binding to the UO₂²⁺ unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim to establish structure–property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. As a result, these materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery.

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Research Organization:: Ames Lab., Ames, IA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1240910

Report Number(s):: IS-J-8330

Journal Information:: Chemistry - A European Journal, Vol. 20, Issue 21; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
uranium
ionic liquids
crystal structure
IR spectroscopy
DFT

CCDC 992824: Experimental Crystal Structure Determination: ZODGAC : 3-n-Butyl-1-methyl-1H-imidazol-3-ium tris(diethylcarbamodithioato)-dioxo-uranium Yaprak, Damla; Spielberg, Eike T.; Bäcker, Tobias https://doi.org/10.5517/cc12b3l3 The current record is supplemented by this dataset	dataset	March 2014
CCDC 992825: Experimental Crystal Structure Determination: ZODGIK : 1-n-Butyl-1-methylimidazol-3-ium tris(ethyl(propyl)carbamodithioato)-dioxo-uranium Yaprak, Damla; Spielberg, Eike; Bäcker, Tobias https://doi.org/10.5517/cc12b3m4 The current record is supplemented by this dataset	dataset	March 2014
CCDC 992826: Experimental Crystal Structure Determination: ZODGUW : 1-n-Butyl-3-methylimidazol-3-ium dioxo-tris(piperidine-1-carbodithioato)-uranium Yaprak, Damla; Spielberg, Eike; Bäcker, Tobias https://doi.org/10.5517/cc12b3n5 The current record is supplemented by this dataset	dataset	March 2014
CCDC 992827: Experimental Crystal Structure Determination: ZODHAD : 1-n-Butyl-3-methylimidazol-3-ium tris(azepane-1-carbodithioato)-dioxo-uranium Yaprak, Damla; Spielberg, Eike; Bäcker, Tobias https://doi.org/10.5517/cc12b3p6 The current record is supplemented by this dataset	dataset	March 2014
CCDC 992828: Experimental Crystal Structure Determination: ZODHEH : 3-n-Butyl-1-methylimidazol-3-ium tris(azocane-1-carbodithioato)-dioxo-uranium Yaprak, Damla; Spielberg, Eike T.; Bäcker, Tobias https://doi.org/10.5517/cc12b3q7 The current record is supplemented by this dataset	dataset	March 2014
CCDC 992829: Experimental Crystal Structure Determination: ZODGEG : 1-n-Butyl-3-methylimidazol-3-ium tris(methyl(propyl)carbamodithioato)-dioxo-uranium Space Group: C 2/c (15), Cell: a 16.582(3)Å b 14.280(3)Å c 28.438(6)Å, α 90.00° β 97.67(3)° γ 90.00° Yaprak, Damla; Spielberg, Eike T.; Backer, Tobias https://doi.org/10.5517/cc12b3r8 The current record is supplemented by this dataset	dataset	March 2014
CCDC 992830: Experimental Crystal Structure Determination: ZODGOQ : 1-n-Butyl-3-methylimidazol-3-ium dioxo-tris(pyrrolidine-1-carbodithioato)-uranium Yaprak, Damla; Spielberg, Eike T.; Bäcker, Tobias https://doi.org/10.5517/cc12b3s9 The current record is supplemented by this dataset	dataset	March 2014