Maximum filling principle and sublattices of actinide atoms in crystal structures

Сережкин, В. Н.; Verevkin, A. G.; Pushkin, D. V.; Сережкина, Л. Б.

doi:10.1134/s1070328408030135

Cited by 32 publications

(5 citation statements)

References 5 publications

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“…An increase in size of the car boxylate ion is accompanied by an increase in the degree of sphericity of VDP (for a sphere, G 3 = 0.077), as well as in the shortest distance between uranium atoms in the structure (Table 7). Despite the above dif ferences, in the crystals of all [UO 2 (Х) 2 (H 2 O) 2 ] dicar boxylates discussed, the VDPs of atoms have a shape of Fedorov cuboctahedron, which is the most abun dant type of polyhedron in the U subshells of the ura nium compounds studied [25].…”

Section: Resultsmentioning

confidence: 92%

First uranyl methacrylate complexes: Synthesis and structure

Сережкина¹,

Григорьев

Shimin³

et al. 2015

Russ. J. Inorg. Chem.

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Crystals of UO 2 (mac) 2 · 2H 2 O (I), UO 2 (mac) 2 · 1.5Dmur (II), and UO 2 (mac) 2 · Tmur (III) (macis methacrylate ion C 3 H 5 COO -, Dmur is N,N dimethylurea, Tmur is tetramethylurea) have been synthe sized and studied by X ray crystallography and IR spectroscopy. The structural units of I are mononuclear [UO 2 (mac) 2 (H 2 O) 2 ] complexes classified with crystal chemical group (A = B 01 = mac -, M 1 = H 2 O). Structure II contains two types of mononuclear uranium containing complexes: cationic [UO 2 (mac)(Dmur) 3 ] + and anionic [UO 2 (mac) 3 ] -. The crystal chemical formula of II is + (A = B 01 = mac -, M 1 = Dmur). The basic structural units of crystal structure III are [UO 2 (mac) 2 (Tmur)] 2 dimers belonging to crystal chemical group AB 2 B 01 M 1 of uranyl complexes (A = B 2 and B 01 = mac -, M 1 = Tmur). The composition and possible structures of 14 stable uranyl com plexes that can form in the -mac --L-H 2 O system (L is Dmur or Tmur) have been determined on the basis of Voronoi-Dirichlet polyhedron characteristics with the use of the 18 electron rule. It has been dem onstrated that, in crystals I-III, uranium containing complexes are combined into a framework through a system of hydrogen bonds and electrostatic and noncovalent interactions.

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Section: Resultsmentioning

confidence: 92%

First uranyl methacrylate complexes: Synthesis and structure

Сережкина¹,

Григорьев

Shimin³

et al. 2015

Russ. J. Inorg. Chem.

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“…Finally, the strictest characteristic showing different packing motifs is the combinatorial‐topological type ( CTT ) of polyhedra, depicting the number of faces of VD polyhedra with given number of vertices. Thus, the VD polyhedra of both U atoms in U‐substructure of compound 1 which does not feature clustering have 14 faces and belong to a widespread CTT [4 4 5 4 6 6 ]‐2, designating that these VD polyhedra have four quadrangular, four pentagonal and six hexagonal faces . On the other hand, the VD polyhedra of U atoms in U‐substructures of compounds 2–4 feature odd numbers of faces (13 or 15) and are very rare .…”

Section: Resultsmentioning

confidence: 99%

Uranyl Coordination Compounds with Alkaline Earth Metals and Crotonate Ligands

et al. 2019

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Crystal structures of three new uranyl compounds were solved using single crystal X‐ray diffraction and studied using FTIR spectroscopy. Although the syntheses conditions were very similar differing only in the alkaline earth metal (Mg, Ca or Sr), the resulting structures are different, containing, respectively, mono‐, tri‐ and hexanuclear metal‐containing building units. This fact proves the profound crystal‐chemical role of secondary metal atoms on the formation of crystal structures. Parameters of alkaline earth metal cations in the three newly synthesized compounds as well as in the earlier reported Ba‐containing analog are discussed in detail using Voronoi–Dirichlet polyhedra and the method of intersecting spheres. Differences in packing of building units in the four mentioned compounds, as well as inter‐ and intramolecular noncovalent interactions in their structures are reported. The results of analysis are consistent with the stereoatomic model of crystal structures.

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“…Actinide chalcogenides are an intriguing class of compounds with extensive compositional and structural diversity that, due to the presence of 5f electrons, exhibit a wide variety of exotic physical properties. − The 5f electrons occupy an intermediate position between the more itinerant 3d and the more localized 4f electrons, resulting in the complex behavior of 5f electrons with respect to bonding to the surrounding atoms. This feature of the actinide elements plays a critical role in the reaction chemistry of the actinides as well as in the fundamental properties of actinide compounds, some of which exhibit superconductivity and complex magnetism. − Due to the actinide contraction across the actinide series, the hardness of the actinide elements increases, making their compounds with soft bases, such as chalcogenides, less favorable compared to oxide compositions. , This increasing oxophilicity creates additional challenges for the synthesis of actinide chalcogenide compounds, aside from the general increase in the radioactivity (shorter half-lives) of the heavier elements.…”

Section: Introductionmentioning

confidence: 99%

Transuranium Sulfide via the Boron Chalcogen Mixture Method and Reversible Water Uptake in the NaCuTS₃ Family

et al. 2022

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The behavior of 5f electrons in soft ligand environments makes actinides, and especially transuranium chalcogenides, an intriguing class of materials for fundamental studies. Due to the affinity of actinides for oxygen, however, it is a challenge to synthesize actinide chalcogenides using non-metallic reagents. Using the boron chalcogen mixture method, we achieved the synthesis of the transuranium sulfide NaCuNpS3 starting from the oxide reagent, NpO2. Via the same synthetic route, the isostructural composition of NaCuUS3 was synthesized and the material contrasted with NaCuNpS3. Single crystals of the U-analogue, NaCuUS3, were found to undergo an unexpected reversible hydration process to form NaCuUS3·xH2O (x ≈ 1.5). A large combination of techniques was used to fully characterize the structure, hydration process, and electronic structures, specifically a combination of single crystal, powder, high temperature powder X-ray diffraction, extended X-ray absorption fine structure, infrared, and inductively coupled plasma spectroscopies, thermogravimetric analysis, and density functional theory calculations. The outcome of these analyses enabled us to determine the composition of NaCuUS3·xH2O and obtain a structural model that demonstrated the retention of the local structure within the [CuUS3]− layers throughout the hydration–dehydration process. Band structure, density of states, and Bader charge calculations for NaCuUS3, NaCuUS3·xH2O, and NaCuNpS3 along with X-ray absorption near edge structure, UV–vis–NIR, and work function measurements on ACuUS3 (A = Na, K, and Rb) and NaCuUS3·xH2O samples were carried out to demonstrate that electronic properties arise from the [CuTS3]− layers and show surprisingly little dependence on the interlayer distance.

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Maximum filling principle and sublattices of actinide atoms in crystal structures

Cited by 32 publications

References 5 publications

First uranyl methacrylate complexes: Synthesis and structure

First uranyl methacrylate complexes: Synthesis and structure

Uranyl Coordination Compounds with Alkaline Earth Metals and Crotonate Ligands

Transuranium Sulfide via the Boron Chalcogen Mixture Method and Reversible Water Uptake in the NaCuTS₃ Family

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Maximum filling principle and sublattices of actinide atoms in crystal structures

Cited by 32 publications

References 5 publications

First uranyl methacrylate complexes: Synthesis and structure

First uranyl methacrylate complexes: Synthesis and structure

Uranyl Coordination Compounds with Alkaline Earth Metals and Crotonate Ligands

Transuranium Sulfide via the Boron Chalcogen Mixture Method and Reversible Water Uptake in the NaCuTS3 Family

Contact Info

Product

Resources

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Transuranium Sulfide via the Boron Chalcogen Mixture Method and Reversible Water Uptake in the NaCuTS₃ Family