Trends and new directions in the crystal chemistry of actinide oxo-clusters incorporated in polyoxometalates

Dufaye, Maxime; Duval, Sylvain; Loiseau, Thierry

doi:10.1039/d0ce00088d

Cited by 20 publications

(17 citation statements)

References 86 publications

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“…The first, common type accommodates typical transition metal cations , or even metal clusters . The second, less common type can adopt only metals with CN 7 (pentagonal bypiramide), such as “yl” cations {(O)Nb(H 2 O)} 3+ and UO 2 2+ . ,,, For each type, full occupancy is eight. In 1 , Pt(IV), being strictly octahedral, occupies only the common sites around the central cavity of the macrocyclic cavitand.…”

Section: Resultsmentioning

confidence: 99%

Coordination of Pt(IV) by {P₈W₄₈} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies

et al. 2022

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Hydrothermal reaction of a macrocyclic inorganic POM cavitand Li17(NH4)21H2[P8W48O184] with [Pt(H2O)2(OH)4] results in coordination of up to six {Pt(H2O) x (OH)4–x } fragments to the internal surface of the polyoxoanion. The product was isolated as K22(NH4)9H3[{Pt(OH)3(H2O)}6P8W48O184]·79H2O (1) and characterized by multiple techniques in the solid state (SCXRD, XRPD, XPS, FTIR, and TGA) and in solution (NMR, ESI-MS, and HPLC-ICP-AES). Electrochemical properties were studied both in solution and as components of the paste electrode. The complex shows electrocatalytic activity in water oxidation.

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Section: Resultsmentioning

confidence: 99%

Coordination of Pt(IV) by {P₈W₄₈} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies

et al. 2022

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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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“…The chemistry of actinide oxo clusters has received increasing attention in the last decades, 1 not only because of their potential application in the nuclear-fuel cycle technologies, catalysis and the design of molecular magnets, but also thanks to the advances in quantum chemistry methods enabling to handle actinide systems with a high density of electronic states arising from degeneracy or near degeneracy of orbitals and treat relativistic effects at the same time. [2][3][4] Actinide oxo/hydroxo clusters provide useful models for the nanosized species involved in spent nuclear fuel separation and the migration behaviour of actinide metals in the environment.…”

Section: Introductionmentioning

confidence: 99%

Decisive Role of 5f-Orbital Covalence in the Structure and Stability of Pentavalent Transuranic Oxo [M₆O₈] Clusters

Zhang

et al. 2020

Inorg. Chem.

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Actinide metal oxo clusters are of vital importance in actinide chemistry, as well as in environmental and material sciences. They are ubiquitous in both aqueous and non-aqueous phases, and play key roles in nuclear materials (e.g. nuclear fuel) and nuclear waste management. Despite the importance, our structural understanding of the actinide metal oxo clusters, particularly the transuranic ones, is very limited, due to the experimental challenges such as the high radioactivity. Herein we report a systematic theoretical study on the structures and stabilities of seven actinide metal oxo-hydroxo clusters [An(IV)6O4(OH)4L12] (An: Th to Cm; L: O2CH − ) (1-An) along with their group-4 (Ti, Zr, Hf, Rf) and lanthanide (Ce) counterparts [M(IV)6O4(OH)4L12] (1-M). The work shows the Td-symmetric structures of all the 1-An/M, and suggests the positions of the -OH functional groups, which are experimentally challenging to determine. Furthermore, by removing six electrons from 1-An, we found that the oxidation could happen on the An(IV) metal ions producing [An(V)6O4(OH)4L12] 6+ (2-An; An: Pa, U, Np), or on the O 2− and OH − ligands producing [An(IV)6(O• − )4(OH•)2(OH)2L12] 6+ (3-An; An: Pu, Am, Cm). Based on the 2-An, we constructed a series of tetravalent and pentavalent actinide metal oxo clusters [An(IV)6O14] 4− (4-An) and [An(V)6O14] 2+ (5-An), which proves the feasibility of the highly important pentavalent actinyl clusters for the first time, demonstrates f-orbital's structurally directing role in the formation of linear [O≡An(V)=O] 1+ actinyl ions, and expands the concept of actinyl-actinyl interaction into pentavalent transuranic actinyl clusters.

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Trends and new directions in the crystal chemistry of actinide oxo-clusters incorporated in polyoxometalates

Abstract: This highlight article reports the synthetic methods, the structural topologies and the behaviour of actinide-polyoxometalate species in aqueous solution.

Cited by 20 publications

References 86 publications

Coordination of Pt(IV) by {P₈W₄₈} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies

Coordination of Pt(IV) by {P₈W₄₈} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies

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

Decisive Role of 5f-Orbital Covalence in the Structure and Stability of Pentavalent Transuranic Oxo [M₆O₈] Clusters

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Trends and new directions in the crystal chemistry of actinide oxo-clusters incorporated in polyoxometalates

Abstract: This highlight article reports the synthetic methods, the structural topologies and the behaviour of actinide-polyoxometalate species in aqueous solution.

Cited by 20 publications

References 86 publications

Coordination of Pt(IV) by {P8W48} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies

Coordination of Pt(IV) by {P8W48} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies

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

Decisive Role of 5f-Orbital Covalence in the Structure and Stability of Pentavalent Transuranic Oxo [M6O8] Clusters

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Coordination of Pt(IV) by {P₈W₄₈} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies

Coordination of Pt(IV) by {P₈W₄₈} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies

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

Decisive Role of 5f-Orbital Covalence in the Structure and Stability of Pentavalent Transuranic Oxo [M₆O₈] Clusters