The Bishop’s Visitation

Burns, Arthur F.

doi:10.1093/acprof:oso/9780198207849.003.0002

Cited by 8 publications

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“…Supramolecular assembly has been demonstrated to be a robust and viable route to prepare large single crystals of uranyl-bearing hybrid materials, and it has been used to assemble discrete molecular building units or “tectons” ([UO 2 Cl 4 ] 2– or [UO 2 Br 4 ] 2– , for example) into extended structures via halogen and/or hydrogen bond-donating pyridinium cations. , This strategy is dependent upon the ability to promote a desired and reproducible uranyl tecton that is appropriately functionalized to accept non-covalent interactions. Generation of such a tecton is a challenge in and of itself, owing to the tendency of the uranyl , (and, more broadly, actinyl) cations to hydrolyze to form secondary building units of higher nuclearity.…”

Section: Introductionmentioning

confidence: 99%

Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly

et al. 2017

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Assembly of a family of 12 supramolecular compounds containing [AnOCl] (An = U, Np, Pu), via hydrogen and halogen bonds donated by substituted 4-X-pyridinium cations (X = H, Cl, Br, I), is reported. These materials were prepared from a room-temperature synthesis wherein crystallization of unhydrolyzed and valence-pure [An(VI)OCl] (An = U, Np, Pu) tectons is the norm. We present a hierarchy of assembly criteria based on crystallographic observations and subsequently quantify the strengths of the non-covalent interactions using Kohn-Sham density functional calculations. We provide, for the first time, a detailed description of the electrostatic potentials of the actinyl tetrahalide dianions and reconcile crystallographically observed structural motifs and non-covalent interaction acceptor-donor pairings. Our findings indicate that the average electrostatic potential across the halogen ligands (the acceptors) changes by only ∼2 kJ mol across the AnO series, indicating that the magnitude of the potential is independent of the metal center. The role of the cation is therefore critical in directing structural motifs and dictating the resulting hydrogen and halogen bond strengths, the former being stronger due to the positive charge centralized on the pyridyl nitrogen, N-H. Subsequent analyses using the quantum theory of atoms in molecules and natural bond orbital approaches support this conclusion and highlight the structure-directing role of the cations. Whereas one can infer that Columbic attraction is the driver for assembly, the contribution of the non-covalent interaction is to direct the molecular-level arrangement (or disposition) of the tectons.

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Section: Introductionmentioning

confidence: 99%

Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly

et al. 2017

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“…In order to further analyze the U−Te arrangement among each sheet, we use the method of anion topology, which can represent the topological connection of anions within the sheet. 37 As can be seen from Figure 2 4a. The topology arrangement can be easily described by the graphical approach 41 as based on a regular pcu (primitive cubic lattice) net, shown in Figure 4c.…”

Section: Resultsmentioning

confidence: 77%

“…In all three uranium tellurite compounds, the connection of uranyl cations with tellurium chains creates small hexagonal-shaped cavities that are filled with different A + cations ( A = Na + , K + , and Tl + ). In order to further analyze the U–Te arrangement among each sheet, we use the method of anion topology , which can represent the topological connection of anions within the sheet . As can be seen from Figure , the UO 2 2+ cations in all three compounds are equatorially bonded with four TeO 4 polyhedra.…”

Section: Results and Discussionmentioning

confidence: 99%

Rich Non-centrosymmetry in a Na–U–Te Oxo-System Achieved under Extreme Conditions

et al. 2016

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Two new sodium uranyl tellurites and two new sodium uranyl tellurates have been synthesized from high-temperature/high-pressure conditions and structurally characterized. We demonstrated that crystalline phases, forming in a Na-U-Te system under extreme conditions, appear to favorably have non-centrosymmetric structures. Three out of four novel uranyl tellurium compounds, Na[(UO2)Te(IV)2O5(OH)], Na2[(UO2)(Te(VI)2O8)], and Na2[(UO2)Te(VI)O5], crystallize in non-centrosymmetric space groups. The crystal structure of Na[(UO2)Te(IV)2O5(OH)] is based on two-dimensional [UO2Te2O5(OH)](-) corrugated sheets, which are charge balanced by guest Na(+) cations. The structure of Na2[(UO2)Te(VI)2O8] is constructed from [(UO2)2Te2O8](2+) anionic layers composed of UO7 pentagonal bipyramids and TeO6 octahedra. Na2[(UO2)(Te(VI)O5)] is a new type of three-dimensional anionic open framework built from the interconnection of UO7 pentagonal bipyramids and TeO6 octahedra with different types of interlacing channels within the U-Te anionic framework. Na[(UO2)Te(IV)6O13(OH)], as the only centrosymmetric compound isolated in the Na-U-Te family, is crystallized in space group Pa3̅, and its structure is highly related to that of cliffordite (UO2(Te3O7)), which is composed from UO8 hexagonal bipyramids and TeO5 square pyramids. The vibrational modes associated with U-O, Te(IV)-O, and Te(VI)-O bonds are discussed, and the Raman spectra of the four compounds are characterized for signature bands.

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“…The continuing efforts of the inorganic research community − have ensured that uranium crystal chemistry remains a vibrant field of research, partly because of the rich crystal chemistry offered by uranium , and partly due to the continuing need for a viable long-term nuclear waste storage solution. The redox chemistry of uranium is of particular interest to the zur Loye group, which probes the conditions under which hexavalent uranium can (or can not) be reduced to tetravalent uranium. − Furthermore, the exploration of the bonding motifs of uranium in the presence of various anions, particularly fluorine, − is of general interest due to the use of uranium fluorides in the processing of nuclear fuel, followed by their subsequent conversion to oxides as the final fuel species.…”

Section: Introductionmentioning

confidence: 99%

[Co(H₂O)₆]₃[U₂O₄F₇]₂: A Model System for Understanding the Formation of Dimensionally Reduced Materials

Felder

Smith

Loye

2018

Crystal Growth & Design

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A cobalt containing mixed-anion uranyl oxidefluoride was synthesized using a mild hydrothermal crystal growth method. The uranyl ions are condensed into a onedimensional chain motif separated by isolated cobalt hexa-aqua centers. The 1-D uranyl material was characterized by singlecrystal and powder X-ray diffraction. The optical, thermal, and magnetic properties were studied and are reported herein. Using the reported composition as a model, a system was derived to predict the dimensionality of hypothetical structures to advance our ability to rationally predict solid-state materials.

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The Bishop’s Visitation

Cited by 8 publications

References 0 publications

Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly

Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly

Rich Non-centrosymmetry in a Na–U–Te Oxo-System Achieved under Extreme Conditions

[Co(H₂O)₆]₃[U₂O₄F₇]₂: A Model System for Understanding the Formation of Dimensionally Reduced Materials

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The Bishop’s Visitation

Cited by 8 publications

References 0 publications

Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly

Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly

Rich Non-centrosymmetry in a Na–U–Te Oxo-System Achieved under Extreme Conditions

[Co(H2O)6]3[U2O4F7]2: A Model System for Understanding the Formation of Dimensionally Reduced Materials

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[Co(H₂O)₆]₃[U₂O₄F₇]₂: A Model System for Understanding the Formation of Dimensionally Reduced Materials