Crystallization of Uranyl Salts from Dialkylimidazolium Ionic Liquids or Their Precursors

Cocalia, Violina A.; Śmiglak, Marcin; Kelley, Steven P.; Shamshina, Julia L.; Gurău, Gabriela; Rogers, Robin D.

doi:10.1002/ejic.201000162

Cited by 25 publications

(31 citation statements)

References 32 publications

(30 reference statements)

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“…As explained in this paper introduction, only one attempt 31 34 This hypothesis was not discussed by the authors, although the analyzed solutions were rather concentrated in uranium (0.4 M). Moreover, it has been shown that nitrates ions are stronger complexant to uranyl than water in hydrophobic IL, 35 so that the residual water in solution should not be able to compete with a massive concentration of nitrates for the uranyl complexation.…”

Section: -mentioning

confidence: 99%

Evidence for the formation of UO2(NO3)42− in an ionic liquid by EXAFS

et al. 2012

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The complexation between uranium(vi) and nitrate ions in a hydrophobic ionic liquid (IL), namely [BMI][NO(3)] (BMI = 1-butyl-3-methylimidazolium(+)), is investigated by EXAFS spectroscopy. It was performed by dissolution of uranyl nitrate UO(2)(NO(3))(2)·6H(2)O or UO(2)(Tf(2)N)(2) (Tf(2)N = bis(trifluoromethylsulfonyl)imide (CF(3)SO(2))(2)N(-)). The formation of the complex UO(2)(NO(3))(4)(2-) is evidenced.

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Section: -mentioning

confidence: 99%

Evidence for the formation of UO2(NO3)42− in an ionic liquid by EXAFS

et al. 2012

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“…In general, linkage of Ur(X m O n ) 5 polyhedra may proceed not only via edge-but also via corner-sharing. Cs 2 (UO 2 )(NO 3 )Cl 3 is the first purely inorganic uranyl oxohalide containing triangular NO 3 groups strongly bonded to Ur(X m O n ) 5 polyhedra (see also [7,8]). Further systematic attempts of hydrothermal synthesis of new alkali uranyl halides using halides of the heavier alkali metals (K, Rb, Cs) halides in excess as starting materials may lead to the discovery of new structure types with potentially interesting applications.…”

Section: Discussionmentioning

confidence: 99%

Crystal Chemistry of Uranyl Halides Containing Mixed (UO₂)(X_mO_n)₅ Bipyramids (X = Cl, Br): Synthesis and Crystal Structure of Cs₂(UO₂)(NO₃)Cl₃

Nazarchuk

Siidra

Krivovichev

2011

Zeitschrift Für Naturforschung B

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Single crystals of Cs 2 (UO 2 )(NO 3 )Cl 3 were prepared by a hydrothermal method at 205 • C. The crystal structure has been solved by Direct Methods: monoclinic, P2 1 /n, a = 10.3748(13), b = 9.4683(13), c = 12.5535 (16)Å, β = 110.280(2) • , V = 1156.7(3)Å 3 , R 1 = 0.029. In the structure, strongly bonded linear uranyl cations UO 2 2+ are equatorially coordinated by two O and three Cl atoms to form (UO 2 )Cl 3 O 2 pentagonal bipyramids. Each bipyramid shares its O-O edge with an adjacent (NO 3 ) − anion to form finite clusters with the chemical composition [(UO 2 )(NO 3 )Cl 3 ] 2− . The Cs + cations provide three-dimensional connectivity of the structure by forming Cs-O and Cs-Cl contacts to the uranyl nitrate chloride complexes. Related structures of mixed-ligand uranyl halides are compared.

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“…18 The geometrical features of structures (Tables S2−S6, Supporting Information) were calculated with Mercury 3.1 software (Cambridge Crystallographic Data Centre, Cambridge, UK). Hirshfeld Surface Analysis.…”

Section: Crystal Growth and Designmentioning

confidence: 99%

“…Compounds with [(UO 2 ) 2 (μ-OH) 2 (NO 3 ) 4 ] 2− anions have been extensively studied with various countercations, such as imidazolium, 18,20 ammonium, 74 and pyridinium. 75 The compound 1 [Bmim] + cations with G′T and TE′ conformations, which maintain specific cation−anion interactions (Table S3, Supporting Information), could be compared with previous well-illustrated structures 18 (Table S3, Supporting Information). As shown in Figure 2b, the [Bmim] + cation with the G′T conformation formed one C− H···O bri , one C−H···O fre , and two C−H···O coo .…”

Section: Crystal Growth and Designmentioning

confidence: 99%

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Crystallization in Ionic Liquids: Synthesis, Properties, and Polymorphs of Uranyl Salts

Liu

2014

Crystal Growth & Design

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Crystallizations in uranyl-containing ionic liquids yielding crystals {X} a {[UO 2 ] b [Y] c } with selected anions and cations (X = [Bmim] + for Y = Cl − , NO 3 − , and SCN − ; Y = Cl − for X = [Emim] + , [Emmim] + , [Bmim] + , and [Bmmim] + ;Emim = l-ethyl-3-methyl-imidazolium, Emmim = l-ethyl-2,3-dimethylimidazolium, Bmim = l-butyl-3-methylimidazolium, and Bmmim = l-butyl-2,3-dimethylimidazolium) were performed herein. Through standard crystallographic analyses, Hirshfeld surface analyses, and multiple characterization techniques, compounds with common cations/anions were investigated. For compounds [Bmim] 2 [(UO 2 ) 2 (μ-OH) 2 (NO 3 ) 4 ] (1), [Bmim] 3 [UO 2 (NCS) 5 ] (2), and [Bmim] 2 [UO 2 Cl 4 ] (3TT and 3TG), common [Bmim] + cations with different conformations were studied with respect to packing and interactions (for 1). The coordinated [(UO 2 ) 2 (μ-OH) 2 (NO 3 ) 4 ] 2− , [UO 2 (NCS) 5 ] 3− , and [UO 2 Cl 4 ] 2− anions that have historically been related to nuclear fuel cycles were demonstrated with respect to geometry and distortion. For compounds with common [UO 2 Cl 4 ] 2− anions [Emim] 2 [UO 2 Cl 4 ] (4), [Emmim] 2 [UO 2 Cl 4 ] (5), [Bmmim] 2 [UO 2 Cl 4 ] (6), 3TT, and 3TG, observed interionic interactions that have been previously impeded by limited structural information were discussed fully in relation to different cations and temperatures. Moreover, multistep phase transformations of 2, which have been undefined in solution studies, have been identified through differential scanning calorimetry analyses and polarizing optical microscopy. The polymorph transformations between 3TT and 3TG in solution, as controlled by uranyl concentration, were studied using optical microscopy and powder X-ray diffraction. The thermal stability, IR/Raman, and UV−vis/luminescence spectra of these compounds were also investigated. ■ INTRODUCTIONIonic liquids (ILs) are attractive to investigators due to their unique physical and chemical properties and have thus been widely examined in many areas. 1,2 Among their usages, crystallization in ILs is a complex and fascinating field of research. 3−5 Both the unique coordination features that cannot generally be observed using molecular solvents and the interaction specifics that are difficult to obtain in the liquid state of ILs can be investigated. 6,7 However, the crystallography data that have immensely promoted our understanding of intermolecular interactions 8 have not been fully explored regarding the crystallographic potential in IL systems.A special interest in f metal-containing ILs has recently arisen in various fields, resulting in many high-quality investigations involving crystallographic studies. 9−12 Specifically, promising applications of ILs in nuclear fuel cycles 13−17 have encouraged extensive studies on uranium-based IL systems, including the relatively common crystallization of uranium salts in ILs and novel explorations of crystallization methods in such complex systems. [3][4][5][6]13,18,19 Using the widely studied uranyl-imidazolium structures as...

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Crystallization of Uranyl Salts from Dialkylimidazolium Ionic Liquids or Their Precursors

Cited by 25 publications

References 32 publications

Evidence for the formation of UO2(NO3)42− in an ionic liquid by EXAFS

Evidence for the formation of UO2(NO3)42− in an ionic liquid by EXAFS

Crystal Chemistry of Uranyl Halides Containing Mixed (UO₂)(X_mO_n)₅ Bipyramids (X = Cl, Br): Synthesis and Crystal Structure of Cs₂(UO₂)(NO₃)Cl₃

Crystallization in Ionic Liquids: Synthesis, Properties, and Polymorphs of Uranyl Salts

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Crystallization of Uranyl Salts from Dialkylimidazolium Ionic Liquids or Their Precursors

Cited by 25 publications

References 32 publications

Evidence for the formation of UO2(NO3)42− in an ionic liquid by EXAFS

Evidence for the formation of UO2(NO3)42− in an ionic liquid by EXAFS

Crystal Chemistry of Uranyl Halides Containing Mixed (UO2)(XmOn)5 Bipyramids (X = Cl, Br): Synthesis and Crystal Structure of Cs2(UO2)(NO3)Cl3

Crystallization in Ionic Liquids: Synthesis, Properties, and Polymorphs of Uranyl Salts

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Crystal Chemistry of Uranyl Halides Containing Mixed (UO₂)(X_mO_n)₅ Bipyramids (X = Cl, Br): Synthesis and Crystal Structure of Cs₂(UO₂)(NO₃)Cl₃