The role of 1-ethyl-3-methylimidazolium diethyl phosphate ionic liquid in uranyl phosphate compounds

Kohlgruber, Tsuyoshi A.; Mackley, Stephanie A.; Bo, Fabrice Dal; Aksenov, Sergey M.; Burns, Peter C.

doi:10.1016/j.jssc.2019.120938

Cited by 6 publications

(13 citation statements)

References 66 publications

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“…Given the nature of ionic liquids, which are defined as materials composed of ionic species that are fluid below 100 °C, they have the potential to act as both a solvent and a templating agent through their organic-based cations . However, to date ionothermal synthesis methods have been applied to produce only relatively few uranyl compounds. − The specific roles of each reagent and heat treatment strategy relative to the final product in these syntheses have not been rigorously explored.…”

Section: Introductionmentioning

confidence: 99%

Effect of Ionothermal Conditions on the Crystallization of Organically Templated Uranyl Sulfate Compounds

Kohlgruber

Felton

Perry

et al. 2021

Crystal Growth & Design

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Seven novel uranyl sulfate compounds were crystallized by ionothermal synthesis methods through systematic changes in experimental conditions. The parameters explored were temperature, soak time, cooling rate, and reactants, including uranium(VI) salt, a uranium(VI) concentration in the ionic liquid, and the pH by cosolvent addition. The ionic liquid 1-ethyl-3-methylimidazolium ethyl sulfate (EMIm-EtSO4) was used in each experiment. Although the seven uranyl sulfate compounds all contained the EMIm organic cation of the ionic liquid, the different synthetic conditions produced varying uranyl coordination environments that resulted in discrete crystal structures. The impact of the ionothermal synthetic conditions on the resulting crystal structures is discussed.

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Section: Introductionmentioning

confidence: 99%

Effect of Ionothermal Conditions on the Crystallization of Organically Templated Uranyl Sulfate Compounds

Kohlgruber

Felton

Perry

et al. 2021

Crystal Growth & Design

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“…Reactions here using the ionic liquid EMIm‐Et 2 PO 4 produced no new reportable compounds. Four compounds were identified (Table S1), three of which were previously reported [38] and one that appeared to have a novel unit cell but that diffracted too poorly to obtain an entirely reliable structural model. The preliminary data of the new crystal structure and unit cell parameters are in Figure S6.…”

Section: Discussionmentioning

confidence: 99%

“…The preliminary data of the new crystal structure and unit cell parameters are in Figure S6. While two studies used EMIm‐Et 2 PO 4 in syntheses previously, the synthetic conditions were quite different from those utilized here [38,41] . Syntheses using EMIm‐Et 2 PO 4 were performed to compare the products with those of the other two ionic liquids to explore the role of the organic functional groups more systematically.…”

Section: Discussionmentioning

confidence: 99%

“…Crystal structures where uranyl ions coordinate only dibutyl phosphate ligands have chain structures different from those observed in parsonsite, while uranyl coordination to dibutyl phosphate, nitrate, and tributyl phosphine oxide leads to dimeric units. [37] Organophosphates with shorter carbon chains than butyl (i. e. ethyl and methyl groups) can be useful analogs to study, as they can coordinate and crystallize similar chains [38] and dimers. [39,40] Previously in our group, we used an imidazolium-based ionic liquid with the diethyl phosphate anion to synthesize novel uranyl phosphate compounds with structural units unique to uranyl phosphate chemistry.…”

Section: Introductionmentioning

confidence: 99%

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Exploring the Role of Organic Functional Groups in the Ionothermal Synthesis of Uranyl Phosphate Materials

Kohlgruber

Felton

Traustason

et al. 2022

Zeitschrift anorg allge chemie

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Four new hybrid organic‐inorganic uranyl phosphate compounds were structurally characterized after single crystals were grown via ionothermal synthesis using the ionic liquids 1‐ethyl‐3‐methylimidazolium dimethyl phosphate and 1‐ethyl‐3‐methylimidazolium dibutyl phosphate. Three of the new crystal structures presented here incorporate dimethyl or monomethyl phosphate ligands into the structural unit to form one chain‐based compound and two sheet‐based compounds. One of the structures utilizes dibutyl phosphate to form a previously reported uranyl compound, a structural polymorph that crystallized in space group P21/c in contrast to the previously reported P‐1 structure. The structural and topological relationships are compared to those of uranyl phosphate minerals as well as previously reported organophosphate compounds. The roles of the organics on the phosphate anions in impacting uranyl coordination and stabilizing the crystal structures are discussed.

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“…The chains of the same topology were found in the crystal structure of derriksite, Cu 4 [UO 2 (SeO 3 ) 2 ](OH) 6 . 41 Similar chains are also observed in the crystal structures of compounds with different organic bridging ligands including phenylphosphinate, 42 diethylphosphate, 43 benzoate, and their derivatives. 44−47 Moreover, such chains can act as building blocks for 2D structural units as, for example, in the uranyl and neptunyl aromatic dicarboxylates.…”

Section: Structural Comparisons and Topological Analysismentioning

confidence: 99%

Secondary Role of Aliphatic and Heterocyclic Amines in the Formation of Low-Temperature Amine-Bearing U, Np, and Pu(VI) Chromates

et al. 2021

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Uranyl compounds with tetrahedral oxoanions demonstrate a significant structural and topological diversity. Complexes of transuranium elements with such anions are not equally well-represented in the literature. To answer the question about the structural similarity in a series of An6+ complexes with XO4 2– anions, we synthesized and studied 10 new U, Np, and Pu chromates with outer-sphere organic cations. The structural analysis and comparison with the literature data shows that the Np and Pu complexes are generally based on the same structural blocks as the uranyl compounds. Moreover, the chromate anion does not show any unique structural role as compared to the sulfate and selenate ions. As a result, the neptunium and plutonium chromates contain 1D and 2D structural units similar to those found in the uranyl sulfates and selenates. The templating role of the outer-sphere cations in the actinyl complexes with tetrahedral oxoanions is also not evident, and there is no clear correlation between the nature of the outer-sphere cations and the topology of the structural units.

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The role of 1-ethyl-3-methylimidazolium diethyl phosphate ionic liquid in uranyl phosphate compounds

Cited by 6 publications

References 66 publications

Effect of Ionothermal Conditions on the Crystallization of Organically Templated Uranyl Sulfate Compounds

Effect of Ionothermal Conditions on the Crystallization of Organically Templated Uranyl Sulfate Compounds

Exploring the Role of Organic Functional Groups in the Ionothermal Synthesis of Uranyl Phosphate Materials

Secondary Role of Aliphatic and Heterocyclic Amines in the Formation of Low-Temperature Amine-Bearing U, Np, and Pu(VI) Chromates

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