A roadmap to uranium ionic liquids: Anti-crystal engineering
Abstract
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.
- Authors:
-
- Ruhr-Univ. Bochum (Germany)
- Univ. zu Koln, Koln (Germany)
- Ruhr-Univ. Bochum (Germany); Ames Lab., Ames, IA (United States)
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1240910
- Report Number(s):
- IS-J-8330
Journal ID: ISSN 0947-6539
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Volume: 20; Journal Issue: 21; Journal ID: ISSN 0947-6539
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; uranium; ionic liquids; crystal structure; IR spectroscopy; DFT
Citation Formats
Yaprak, Damla, Spielberg, Eike T., Bäcker, Tobias, Richter, Mark, Mallick, Bert, Klein, Axel, and Mudring, Anja -Verena. A roadmap to uranium ionic liquids: Anti-crystal engineering. United States: N. p., 2014.
Web. doi:10.1002/chem.201303333.
Yaprak, Damla, Spielberg, Eike T., Bäcker, Tobias, Richter, Mark, Mallick, Bert, Klein, Axel, & Mudring, Anja -Verena. A roadmap to uranium ionic liquids: Anti-crystal engineering. United States. https://doi.org/10.1002/chem.201303333
Yaprak, Damla, Spielberg, Eike T., Bäcker, Tobias, Richter, Mark, Mallick, Bert, Klein, Axel, and Mudring, Anja -Verena. Tue .
"A roadmap to uranium ionic liquids: Anti-crystal engineering". United States. https://doi.org/10.1002/chem.201303333. https://www.osti.gov/servlets/purl/1240910.
@article{osti_1240910,
title = {A roadmap to uranium ionic liquids: Anti-crystal engineering},
author = {Yaprak, Damla and Spielberg, Eike T. and Bäcker, Tobias and Richter, Mark and Mallick, Bert and Klein, Axel and Mudring, Anja -Verena},
abstractNote = {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.},
doi = {10.1002/chem.201303333},
journal = {Chemistry - A European Journal},
number = 21,
volume = 20,
place = {United States},
year = {Tue Apr 15 00:00:00 EDT 2014},
month = {Tue Apr 15 00:00:00 EDT 2014}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 15 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Carboxyl-Functionalized Task-Specific Ionic Liquids for Solubilizing Metal Oxides
journal, November 2008
- Nockemann, Peter; Thijs, Ben; Parac-Vogt, Tatjana N.
- Inorganic Chemistry, Vol. 47, Issue 21
Solidification of Ionic Liquids: Theory and Techniques
journal, January 2010
- Mudring, Anja-Verena
- Australian Journal of Chemistry, Vol. 63, Issue 4
Chemistry of the uranyl group. III. Preparation, properties, and crystal structure of the isomorphous pair UO2((C2H5)3NCS2)2(C6H5)3AsO and UO2((C2H5)2NCS2)2(C6H5)3PO
journal, September 1970
- Graziani, Rodolfo; Zarli, B.; Cassol, Alberto
- Inorganic Chemistry, Vol. 9, Issue 9
Ionic Liquids for Lanthanide and Actinide Chemistry
journal, May 2010
- Mudring, Anja-Verena; Tang, Sifu
- European Journal of Inorganic Chemistry, Vol. 2010, Issue 18
Crystal engineering. From molecules to materials
journal, August 2003
- Desiraju, Gautam R.
- Journal of Molecular Structure, Vol. 656, Issue 1-3
Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988
- Becke, A. D.
- Physical Review A, Vol. 38, Issue 6
Correlation between the vibronic spectra of the uranyl ion and the geometry of its coordination
journal, February 1972
- Görller-Walrand, C.; De Jaegere, S.
- Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 28, Issue 2
Uranium separation from high iron concentration by the use of ammonium pyrrolidine dithiocarbamate
journal, March 1989
- Nagj, M.; Stergaršek, A.; Injuk, J.
- Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 130, Issue 1
Chelating resin functionalized with dithiocarbamate for the recovery of uranium from seawater
journal, September 1984
- Tabushi, Iwao; Kobuke, Yoshiaki; Nakayama, Noritake
- Industrial & Engineering Chemistry Product Research and Development, Vol. 23, Issue 3
The application of novel hydrophobic ionic liquids to the extraction of uranium(vi) from nitric acid medium and a determination of the uranyl complexes formed
journal, January 2011
- Bell, Thomas James; Ikeda, Yasuhisa
- Dalton Transactions, Vol. 40, Issue 39
Uranyl Complexes of Carboxyl-Functionalized Ionic Liquids
journal, April 2010
- Nockemann, Peter; Van Deun, Rik; Thijs, Ben
- Inorganic Chemistry, Vol. 49, Issue 7
Infrared Spectroscopic Studies of some Uranyl Nitrate Complexes
journal, December 1976
- Ohwada, Ken
- Journal of Coordination Chemistry, Vol. 6, Issue 2
Evaluation of long chain dithiocarbamates as photometric reagents for the determination of trace amounts of uranium
journal, April 1995
- Malathi, K.; Subbaiyan, M.
- Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 191, Issue 2
Determination of uranium in sea water by X-ray fluorescence spectroscopy
journal, February 1986
- Nagj, M.; Makjanić, J.; Orlić, I.
- Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 97, Issue 2
Synthesis of bimagnetic ionic liquid and application for selective aerobic oxidation of aromatic alcohols under mild conditions
journal, January 2011
- Miao, Cheng-Xia; Wang, Jin-Quan; Yu, Bing
- Chemical Communications, Vol. 47, Issue 9
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
- Weigend, Florian; Ahlrichs, Reinhart
- Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
Extraction of Uranium from Aqueous Solutions by Using Ionic Liquid and Supercritical Carbon Dioxide in Conjunction
journal, April 2009
- Wang, Joanna Shaofen; Sheaff, Chrystal N.; Yoon, Byunghoon
- Chemistry - A European Journal, Vol. 15, Issue 17
Sodium Trinitratouranylate(VI) Na[UO2(NO3)3]
journal, March 2010
- Bäcker, Tobias; Mudring, Anja-Verena
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 636, Issue 6
An Evaluation of Harmonic Vibrational Frequency Scale Factors
journal, November 2007
- Merrick, Jeffrey P.; Moran, Damian; Radom, Leo
- The Journal of Physical Chemistry A, Vol. 111, Issue 45
Efficient evaluation of three-center two-electron integrals over Gaussian functions
journal, January 2004
- Ahlrichs, Reinhart
- Physical Chemistry Chemical Physics, Vol. 6, Issue 22
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
Thermal behaviour of metal-dithiocarbamates
journal, August 1986
- Sharma, Anand Kumar
- Thermochimica Acta, Vol. 104
Electronic Spectra of Pure Uranyl(V) Complexes: Characteristic Absorption Bands Due to a U V O 2 + Core in Visible and Near-Infrared Regions 1
journal, September 2005
- Mizuoka, Koichiro; Tsushima, Satoru; Hasegawa, Miki
- Inorganic Chemistry, Vol. 44, Issue 18
Crystal Structure of 1-Butyl-3-methylimidazolium Chloride. A Clue to the Elucidation of the Ionic Liquid Structure
journal, August 2003
- Saha, Satyen; Hayashi, Satoshi; Kobayashi, Akiko
- Chemistry Letters, Vol. 32, Issue 8
Temperature dependence of solid uranyl-tris-acetate fluorescence spectra
journal, March 1984
- Szöke, J.
- Journal of Molecular Structure, Vol. 115
Optimized accurate auxiliary basis sets for RI-MP2 and RI-CC2 calculations for the atoms Rb to Rn
journal, January 2007
- Hellweg, Arnim; Hättig, Christof; Höfener, Sebastian
- Theoretical Chemistry Accounts, Vol. 117, Issue 4
Task-Specific Ionic Liquid for Solubilizing Metal Oxides
journal, October 2006
- Nockemann, Peter; Thijs, Ben; Pittois, Stijn
- The Journal of Physical Chemistry B, Vol. 110, Issue 42
Die Wasserstoffbrücke im Festkörper
journal, January 2002
- Steiner, Thomas
- Angewandte Chemie, Vol. 114, Issue 1
Electrochemical Studies on Uranyl(VI) Chloride Complexes in Ionic Liquid, 1-Butyl-3-methylimidazolium Chloride
journal, February 2009
- Ikeda, Yasuhisa; Hiroe, Katsuyuki; Asanuma, Noriko
- Journal of Nuclear Science and Technology, Vol. 46, Issue 2
Identification of the Lower Transitions in the Spectra of Uranyl Complexes
journal, May 1971
- Görller‐Walrand, C.; Vanquickenborne, L. G.
- The Journal of Chemical Physics, Vol. 54, Issue 10
CHEMISTRY: Ionic Liquids--Solvents of the Future?
journal, October 2003
- Rogers, R. D.; Seddon, Kenneth R.
- Science, Vol. 302, Issue 5646, p. 792-793
Task-Specific Ionic Liquids
journal, September 2004
- H. Davis, Jr., James
- Chemistry Letters, Vol. 33, Issue 9
In-Situ Crystal Growth and Properties of the Magnetic Ionic Liquid [C 2 mim][FeCl 4 ]
journal, June 2011
- Bäcker, Tobias; Breunig, Oliver; Valldor, Martin
- Crystal Growth & Design, Vol. 11, Issue 6
Actinide structural studies. Part 17. The crystal and molecular structures of four uranyl(VI) complexes with N,N-dialkyldithiocarbamate ligands
journal, January 1989
- Alcock, Nathaniel W.; Pennington, Mark
- Journal of the Chemical Society, Dalton Transactions, Issue 3
Polysulfonylamine, CLIII [1]. Schwache Wasserstoffbrücken mit aktivierten Methyldonoren: Kristallstrukturen von Cholinium-, Betainium- und Dimethyl[2-(dimethylamino)ethyl]ammonium-dimesylamid Polysulfonylamines, CLIII [1]. Weak Hydrogen Bonding with Activated Methyl Donors: Crystal Structures of Cholinium, Betainium and Dimethyl[2-(dimethylamino)ethyl]ammonium-dimesylamide
journal, May 2002
- Henschel, Dagmar; Moers, Oliver; Wijaya, Karna
- Zeitschrift für Naturforschung B, Vol. 57, Issue 5
Task-Specific Ionic Liquids
journal, March 2010
- Giernoth, Ralf
- Angewandte Chemie International Edition, Vol. 49, Issue 16
Works referencing / citing this record:
Cadmium tris(dithiocarbamate) ionic liquids as single source, solvent-free cadmium sulfide precursors
journal, January 2018
- Macreadie, Lauren K.; Forsyth, Craig M.; Turner, David R.
- Chemical Communications, Vol. 54, Issue 64
Stoichiometry of adamantylamine–trinitrophloroglucinol salts controlled by solvate formation
journal, January 2020
- Smokrović, Kristina; Stilinović, Vladimir
- CrystEngComm, Vol. 22, Issue 10
Synthesis, structural characterization and luminescence properties of 1-carboxymethyl-3-ethylimidazolium chloride
journal, May 2018
- Prodius, Denis; Wilk-Kozubek, Magdalena; Mudring, Anja-Verena
- Acta Crystallographica Section C Structural Chemistry, Vol. 74, Issue 6
A Structural and Spectroscopic Study of the First Uranyl Selenocyanate, [Et4N]3[UO2(NCSe)5]
journal, February 2016
- Nuzzo, Stefano; Browne, Michelle; Twamley, Brendan
- Inorganics, Vol. 4, Issue 1