Uranium(VI) hybrid materials with [(UO2)3(µ3‐O)(µ2‐OH)3]+as the sub–building unit via uranyl–cation interactions

Zhang, Yingjie; Clegg, Jack K.; Lu, Kim; Lumpkin, Gregory R.; Tran, Toan Trong; Aharonovich, Igor; Scales, Nicholas; Li, Feng

doi:10.1002/slct.201500043

Cited by 20 publications

(8 citation statements)

References 97 publications

(13 reference statements)

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“…There are four different coordination modes of the TP 2– ligand in compounds 1 – 6 (Figure S3), and the combination of these four coordination modes leads to five different uranyl networks (Figure ). Although other uranyl- TP networks can also be found, ,− ,− it is still rare to see such a series of template-mediated layered 2D uranyl networks because the complicated hydrolysis of uranyl cations would always result in great variations in the final structures, such as interpenetrating UCPs, zero-dimensional UCPs, one-dimensional UCPs, , and three-dimensional UCPs . Apparently, the consistent layer configuration of uranyl- TP networks in this work has a close relationship with the presence of CB n .…”

Section: Resultsmentioning

confidence: 65%

Noncomplexed Cucurbituril-Mediated Structural Evolution of Layered Uranyl Terephthalate Compounds

Mei

et al. 2019

Inorg. Chem.

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Template synthesis is one of the most feasible ways to explore new uranyl compounds with intriguing structures and properties.Here we demonstrate the preparation of six novel "sandwichlike" uranyl coordination polymers (UCPs) based on two-dimensional uranylterephthalate acid (H 2 TP) networks using CBn (n = 5, 6, 8) as template ligands in the presence of different cations (Na + , K + , Cs + , orof layered uranyl-TP networks with the complex of CB5 and s o d i u m c a t i o n s a s t e m p l a t e l i g a n d s . I n c o m p o u n d 2 ([(UO 2 ) 2 (TP) 3 ] 2 (CB6)(H 2 O) 10 ), CB6 located between uranyl-TP networks contacts them by π−π interactions and hydrogen bonds. Compound 3 ([(UO 2 ) 2 (TP) 3 ] 2 [Na 2 (H 2 O) 10 (CB6)]) is the same as compound 2 except for sodium cations bonding with CB6. Similarly in compound 4 ([(UO 2 ) 2 (TP) 3 ][Cs(H 2 O) 3 (CB6)]), CB6 is a capsulelike structure capped with two cesium cations and interacts with uranyl-TP networks through π−π and C−H•••π interactions. Compound 5 ([(UO 2 ) 2 (TP) 3 (HCOO) consists of both templates of CB6 and CB5 in which each CB5 is capped with one potassium cation while the H 2 N(CH 3 ) 2 + cation is held at CB6 portals. In compound 6), CB8 ligands are connected by cesium cations to form a triangle motif and are further located between the uranyl-TP networks as template agents. All of the 2D layered structures with free CBn or cation-anchored CBn intercalate into the laminates of uranyl-terephthalate and shows a cucurbituril-mediated structural evolution. The regulating role of CBn as structure-directing template agents for the construction of layered UCPs through outer-surface interactions with layers of uranyl terephthalate is demonstrated, especially for the case of CB6 with contractive interlayer spacing.

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Section: Resultsmentioning

confidence: 65%

Noncomplexed Cucurbituril-Mediated Structural Evolution of Layered Uranyl Terephthalate Compounds

Mei

et al. 2019

Inorg. Chem.

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“…Spectral features from chelating ligands were specifically noted for the citrate [16], malate [133], pyromellitate [134], benzenedicarboxylate [135], and hydrobenzoate [136] systems. Similarly, uranyl peroxide spectra contain overlapping modes from uranyl and peroxide stretches.…”

Section: Chemical and Structural Elucidation Of Uranium Solid-state Cmentioning

confidence: 99%

“…Overlapping vibrational modes increase the difficulty of spectral interpretation for coordination compounds and hybrid materials, particularly in the presence of some organic ligands or peroxide molecules. Spectral features from chelating ligands were specifically noted for the citrate [16], malate [133], pyromellitate [134], benzenedicarboxylate [135], and hydrobenzoate [136] systems. Similarly, uranyl peroxide spectra contain overlapping modes from uranyl and peroxide stretches.…”

Section: Chemical and Structural Elucidation Of Uranium Solid-state Cmentioning

confidence: 99%

Detection and identification of solids, surfaces, and solutions of uranium using vibrational spectroscopy

Haes

Forbes

2018

Coordination Chemistry Reviews

132

128

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The purpose of this review is to provide an overview of uranium speciation using vibrational spectroscopy methods including Raman and IR. Uranium is a naturally occurring, radioactive element that is utilized in the nuclear energy and national security sectors. Fundamental uranium chemistry is also an active area of investigation due to ongoing questions regarding the participation of 5f orbitals in bonding, variation in oxidation states and coordination environments, and unique chemical and physical properties. Importantly, uranium speciation affects fate and transportation in the environment, influences bioavailability and toxicity to human health, controls separation processes for nuclear waste, and impacts isotopic partitioning and geochronological dating. This review article provides a thorough discussion of the vibrational modes for U(IV), U(V), and U(VI) and applications of infrared absorption and Raman scattering spectroscopies in the identification and detection of both naturally occurring and synthetic uranium species in solid and solution states. The vibrational frequencies of the uranyl moiety, including both symmetric and asymmetric stretches are sensitive to the coordinating ligands and used to identify individual species in water, organic solvents, and ionic liquids or on the surface of materials. Additionally, vibrational spectroscopy allows for the in situ detection and real-time monitoring of chemical reactions involving uranium. Finally, techniques to enhance uranium species signals with vibrational modes are discussed to expand the application of vibrational spectroscopy to biological, environmental, inorganic, and materials scientists and engineers.

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“…Moreover, the structural similarities are not only restricted to α-hydroxy acids. Further evidence for complexes containing the (UO 2 ) 3 (μ 3 -O)(μ 2 -OR) 3 “core” structure is given by, for example, terephthalate, p -nitrobenzoate, and nucleotides, with the latter containing no carboxyl groups, thus surrounding the motif of interest by the oxygen atoms of both the sugar unit and the phosphate residues, respectively.…”

Section: Discussionmentioning

confidence: 99%

Dimeric and Trimeric Uranyl(VI)–Citrate Complexes in Aqueous Solution

et al. 2021

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This research addresses a subject discussed controversially for almost 70 years. The interactions between the uranyl(VI) ion, U(VI), and citric acid, H3Cit, were examined using a multi-method approach comprising nuclear magnetic resonance (NMR), ultraviolet–visible (UV–vis), attenuated total reflectance Fourier-transform infrared (ATR FT-IR), and extended X-ray absorption fine-structure (EXAFS) spectroscopies as well as density functional theory (DFT) calculations. Combining 17O NMR spectroscopy and DFT calculation provided an unambiguous decision on complex configurations, evidencing for the first time that the dimeric complex, (UO2)2(HCit–H)2 2–, exists as two diastereomers with the syn-isomer in aqueous solution strongly favored over the anti-isomer. Both isomers interconvert mutually with exchange rates of ∼30 s–1 at −6 °C and ∼249 s–1 at 60 °C in acidic solution corresponding to an activation barrier of about 24 kJ mol–1. Upon increasing the pH value, ternary dimeric mono- and bis-hydroxo as well as trimeric complexes form, that is, (UO2)2(HCit–H)2(OH)3–, (UO2)2(HCit–H)2(OH)2 4–, (UO2)3(O)(Cit–H)3 8–, and (UO2)3(O)(OH)(Cit–H)2 5–, respectively. Stability constants were determined for all dimeric and trimeric species, with log β° = −(8.6 ± 0.2) for the 3:3 species being unprecedented. Additionally, in the 6:6 sandwich complex, formed from two units of 3:3 species, the 17O NMR resonance of the trinuclear uranyl(VI) core bridging μ3-O is shown for the first time. Species distribution calculations suggest that the characterized polynuclear U(VI)–citrate species do not significantly increase uranium(VI) mobility in the environment. Furthermore, we revise the misconceptions in the aqueous U(VI)–citric acid solution chemistry, that is, structures proposed and repeatedly taken up, and outline generalized isostructural considerations to provide a basis for future U(VI) complexation studies.

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Uranium(VI) hybrid materials with [(UO₂)₃(µ₃‐O)(µ₂‐OH)₃]⁺as the sub–building unit via uranyl–cation interactions

Cited by 20 publications

References 97 publications

Noncomplexed Cucurbituril-Mediated Structural Evolution of Layered Uranyl Terephthalate Compounds

Noncomplexed Cucurbituril-Mediated Structural Evolution of Layered Uranyl Terephthalate Compounds

Detection and identification of solids, surfaces, and solutions of uranium using vibrational spectroscopy

Dimeric and Trimeric Uranyl(VI)–Citrate Complexes in Aqueous Solution

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