Uranium(VI) coordination polymers with pyromellitate ligand: Unique 1D channel structures and diverse fluorescence

Zhang, Yingjie; Bhadbhade, Mohan; Karatchevtseva, Inna; Price, Jason R.; Liu, Hao; Zhang, Zhaoming; Kong, Linggen; Čejka, Jiří; Lu, Kim; Lumpkin, Gregory R.

doi:10.1016/j.jssc.2015.01.033

Cited by 31 publications

(19 citation statements)

References 45 publications

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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%

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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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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“…However, The most intense band is located at 524 nm, red shifted compared to 510 nm observed for UNH . Such red‐shift effect is related to the presence of pentagonal bipyramidal uranium centres . The emission spectrum of 2 is similar to that of 1 but in a broad nature without any distinguished individual bands.…”

Section: Resultsmentioning

confidence: 76%

“…The emission spectrum of 1 has six distinguishable emission bands at 493 (sh), 506, 524, 552, 575 and 608 nm, similar to those of uranyl nitrate hexahydrate (UNH) with typical bands corresponding to the electronic transitions S 11 → S 00 and S 10 → S 0 ν (ν=0‐4) of the uranyl ion . However, The most intense band is located at 524 nm, red shifted compared to 510 nm observed for UNH . Such red‐shift effect is related to the presence of pentagonal bipyramidal uranium centres .…”

Section: Resultsmentioning

confidence: 93%

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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

Zhang

Clegg

et al. 2016

ChemistrySelect

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The hydrothermal reaction of uranyl nitrate with 1,4‐benzenedicarboxylic acid (H2bdc) in the presence of strontium or potassium hydroxides and nitrates afford the formation of two new uranyl hybrid materials featuring extensive uranyl‐strontium or uranyl‐potassium interactions with [(UO2)3(µ3‐O)(µ2‐OH)3]+ as the sub‐building unit. Sr1.5[(UO2)12(O)3(OH)13(bdc)4]⋅6H2O (1) contains one‐dimensional (1D) uranyl oxohydroxyl ribbons made of trinuclear pentagonal bipyramidal uranyl units. The ribbons are linked together via uranyl‐strontium interactions to form 2D inorganic domains which are further connected through µ4‐bdc anions forming a 3D hybrid structure. This is the first reported uranyl‐strontium interaction in extended hybrid solid with the shortest Sr‐O−yl bond length of 2.596 (8) Å. K3[(UO2)12(O)3(OH)13(bdc)4]⋅8H2O (2) has a similar 3D hybrid structure built up through extensive K‐O−yl interactions with the shortest K‐O−yl bond length of 2.620 (6) Å. Raman spectroscopy has confirmed the presence of oxo‐bridging (U−O−U) vibrations. Thermal stabilities and photoluminescent properties are reported.

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“…Pyromellitic acid (prma, also called 1,2,4,5-benzenetetracarboxylic acid, Figure 50), has a history of use in metal-organic frameworks; its four coordination sites give rise to more flexibility in the system, leading to multi-dimensional frameworks with large channels. [83][84][85] Louiseau et.al. reported the 3D crystal structure of (UO2)2(H2O)2(btec)•H2O in 2012; 78 the yellow rod-shaped crystals are orthorhombic in the Pbcn space group.…”

Section: Pyromellitic Acidmentioning

confidence: 99%

Synthesis of Actinide Materials for the Study of Basic Actinide Science and Rapid Separation of Fission Products

Dorhout

2017

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This dissertation covers several distinct projects relating to the fields of nuclear forensics and basic actinide science. Post-detonation nuclear forensics, in particular, the study of fission products resulting from a nuclear device to determine device attributes and information, often depends on the comparison of fission products to a library of known ratios. The expansion of this library is imperative as technology advances. Rapid separation of fission products from a target material, without the need to dissolve the target, is an important technique to develop to improve the library and provide a means to develop samples and standards for testing separations. Several materials were studied as a proof-of-concept that fission products can be extracted from a solid target, including microparticulate (< 10 µm diameter) dUO2, porous metal organic frameworks (MOFs) synthesized from depleted uranium (dU), and other organicbased frameworks containing dU. The targets were irradiated with fast neutrons from one of two different neutron sources, contacted with dilute acids to facilitate the separation of fission products, and analyzed via gamma spectroscopy for separation yields. The results indicate that smaller particle sizes of dUO2 in contact with the secondary matrix KBr yield higher separation yields than particles without a secondary matrix. It was also discovered that using 0.1 M HNO3 as a contact acid leads to the dissolution of the target material. Lower concentrations of acid were used for future experiments. In the case of the MOFs, a larger pore size in the framework leads to higher separation yields when contacted with 0.01 M HNO3. Different types of frameworks also yield different results. The second portion of this dissertation describes efforts to better understand electronic structure and bonding of the actinide metals in various environments. One project involved studying thorium and uranium bonding with the soft-donor chalcogenides, specifically sulfur. Results from these studies include the synthesis and characterization of the novel (C5Me5)2Th(SMe)2 complex; the synthesis of (C5Me5)2ThS5 by myriad routes, indicating the product is a thermodynamic sink; and evidence that sulfur is inserted iv into the thorium-carbon bond of (C5Me5)2ThMe2 to form the pentasulfide. The second project involved unique activation of the strong carbon-halide bonds present in benzyl-halides mediated by a uranium-(2,2'-bipyridine) complex. The resultant products include a series of uranium-halide bonds from fluoride to iodide, and the addition of the benzyl group to the bipyridine ring. Studies of the mechanism indicate that the benzyl group is added first to the 6 position of the ring before migrating to its final place at the 4 position. The final project utilized a novel gold-tetrazolate complex that can be tailored to add highnitrogen ligands to actinides in a facile and safe way. This transfer ligand was used to synthesize new uranium-tetrazolate species. A brief exploration into using the transfer ligand to add tetra...

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Uranium(VI) coordination polymers with pyromellitate ligand: Unique 1D channel structures and diverse fluorescence

Cited by 31 publications

References 45 publications

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

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

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

Synthesis of Actinide Materials for the Study of Basic Actinide Science and Rapid Separation of Fission Products

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Uranium(VI) coordination polymers with pyromellitate ligand: Unique 1D channel structures and diverse fluorescence

Cited by 31 publications

References 45 publications

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

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

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

Synthesis of Actinide Materials for the Study of Basic Actinide Science and Rapid Separation of Fission Products

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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