{Np<sub>38</sub>} clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides

Martin, Nicolas P.; Volkringer, Christophe; Roussel, Pascal; März, Juliane; Hennig, Christoph; Loiseau, Thierry; Ikeda‐Ohno, Atsushi

doi:10.1039/c8cc03744b

Cited by 36 publications

(39 citation statements)

References 40 publications

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“…In addition to these species, actinide oxide nanoclusters containing 38 actinide cations have been reported for uranium, neptunium, and plutonium . All three {An 38 } nanoclusters contain only bridging oxo ligands and no OH ligands within the core.…”

Section: Figurementioning

confidence: 75%

“…The intermediate nanocluster {U 12 } is stabilized by six benzoate ligands, six glycolate ligands, and three oxalate ligands; charge balance is provided by [UO 2 Cl 4 ] 2− and Cl − . {Np 38 }, the third actinide oxide nanocluster, crystallizes in the tetragonal space group I 4 m from a solvothermal synthesis under inert conditions; either THF or isopropanol serve as the stabilizing ligand …”

Section: Figurementioning

confidence: 99%

“…[14] The observed distortionw ithin {U 16 }m ay be due to the presence of both U V and U IV centers, [14] thoughs ome hexanuclear speciesh ave been reportedt oc ontain distorted octahedral symmetriesa nd only An IV metal centers. [19,22] In addition to these species, actinide oxide nanoclusterscon-taining3 8a ctinide cations have been reported for uranium, [24,25] neptunium, [26] and plutonium. [7,11] All three {An 38 } nanoclusters containo nly bridgingoxo ligandsa nd no OH ligandsw ithin the core.…”

mentioning

confidence: 99%

“…{Np 38 }, the third actinide oxide nanocluster,c rystallizesi nt he tetragonal space group I4m from as olvothermals ynthesis under inert conditions;e ither THF or isopropanol serve as the stabilizing ligand. [26] Te travalent-cation nanoclusters also form in the lanthanide series and yield 'magic numbers' of metal-oxide nanoclusters through the reporteds ynthesis of {Ce 10 }a nd {Ce 22 }. [29] Like {U 16 }, these cerium nanoclusters are mixed-valent, having both Ce III andC e IV metal centers, and require organic capping ligands (isobutyric acid, 1,1,1-tris-(hydroxymethyl)ethane, and Nmethyldiethanolamine) to passivate the surface.…”

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confidence: 99%

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Extension of the Plutonium Oxide Nanocluster Family to Include {Pu₁₆} and {Pu₂₂}

Sigmon

Hixon

2019

Chemistry A European J

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Plutonium(IV) oxide nanoclusters represent an interesting scientific problem regarding structure‐function relationships and are also relevant to global concerns surrounding plutonium reprocessing, the remediation of plutonium‐contaminated soils, and the storage or disposal of plutonium‐containing wastes. Here we report the synthesis of five unique PuIV oxide nanoclusters containing 38, 22, or 16 metal centers and capped only with inorganic ligands, such as chlorine and water, which prevent formation of the extended PuO2 structure. The products are interrogated through single‐crystal X‐ray diffraction, bond valence calculations, and comparisons to other known metal‐oxide nanoclusters. Of particular interest is the incorporation of hydroxide linkages into the smaller plutonium oxide nanoclusters, which underscores previous observations and hypotheses regarding the formation of plutonium polymers and colloids.

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Section: Figurementioning

confidence: 75%

Section: Figurementioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Extension of the Plutonium Oxide Nanocluster Family to Include {Pu₁₆} and {Pu₂₂}

Sigmon

Hixon

2019

Chemistry A European J

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“…Plutonium, for example, has been shown to form large polyoxo clusters ranging from {Pu 16 } to {Pu 38 } oligomers from acidic HCl solutions . Uranium and neptunium similarly form polyoxo clusters; these clusters are often stabilized by organic carboxylates …”

Section: Introductionmentioning

confidence: 99%

Mononuclear to Polynuclear U^IV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation

Vanagas

Higgins

Wacker

et al. 2020

Chemistry A European J

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Uranium(IV)c omplexation by 2-furoic acid (2-FA) was examined to better understand the effects of ligand identity and reactionc onditions on speciesf ormationa nd stability.F ive compounds were isolated:[ UCl 2 (2-FA) 2 (H 2 O) 2 ] n (1), [U 4 Cl 10 O 2 (THF) 6 (2-FA) 2 ]·2THF (2), [U 6 O 4 (OH) 4 (H 2 O) 3 (2-FA) 12 ]·7THF·H 2 O( 3), [U 6 O 4 (OH) 4 (H 2 O) 2 (2-FA) 12 ]·8.76 H 2 O( 4), and [U 38 Cl 42 O 54 (OH) 2 (H 2 O) 20 ]·m H 2 O·n THF (5). The structures were determinedb ys ingle-crystal X-ray diffractiona nd further characterized by Raman, IR, and optical absorption spectroscopy.T he thermals tability and magnetic behavior of the compounds werealso examined. Variationsinthe synthetic conditions led to notable differences in the structural units observed in the solids tate. At low H 2 O/THF ratios, a tetranuclear oxo-bridged [U 4 O 2 ]c ore was isolated.A ging of this solution resulted in the formationaU 38 oxo cluster capped by chloro and water ligands. However,a ti ncreasing water concentrationso nly hexanuclear units wereo bserved. In all cases, at temperatures of 100-120 8C, UO 2 nanoparticles formed.[a] Dr.Supporting information (Structure refinement details;Thermal ellipsoid plots;B ond Valence Summation values;P owderX -ray diffractionpatterns; UV/Vis-NIR spectra;Raman and IR spectra;TGA spectra;M agnetic data; TEM data)a nd the ORCID identification number(s) for the author(s) of this articlecan be foundu nder: https://doi.Figure 5. Binding modes of the 2-FAu nits observed in 3 (a,c,d) and 4 (b-d).

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Metal–Organic Frameworks Based on Group 3 and 4 Metals

et al. 2020

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Metal-organic frameworks (MOFs), a class of porous crystalline framework materials, are linked by strong bonds between inorganic and organic building blocks. [1-3] In the past two decades, MOFs have rapidly grown as a star material due to their exceptional performance in areas such as storage, separation and catalysis. [4] The outstanding performance of MOFs in applications benefits from their intrinsically porous structures and highly tunable pore environment. [5-7] The creation and modification of pore space with optimized size, functionality and diversity can be precisely tuned at the molecular level by rationally designing building blocks and synthetic procedures. [8,9] The diversity of MOFs can be enriched by expanding the library of organic linkers with varying lengths, geometries, and functional groups. [10] Additionally, very diverse metal cations are applied to MOF synthesis, ranging from monovalent (Ag + , Cu + , etc.), divalent (Mg 2+ , Fe 2+ , Co 2+ , Ni 2+ , etc.), trivalent (Al 3+ , Sc 3+ , V 3+ , Cr 3+ , etc.), to tetravalent (Ti 4+ , Zr 4+ , Hf 4+ , etc.) cations. [11] In this review, we mainly focus on MOFs with group 3 and 4 metals, including Y, lanthanides (Ln, from La to Lu), actinides (An, from Ac to Lr), Ti, and Zr (Figure 1). Group 3 metal cations are generally found in the oxidation state of +3 in the MOF structures, while group 4 metal cations mainly exist in the oxidation state of +4, leading to the formation of much stronger coordination bonds with carboxylates. [12] Therefore, group 4 metal-based MOFs (M IV-MOFs) generally have enhanced stability compared with MOFs constructed from metals of group 3 and other groups. This series of MOFs stands out because the involved metals can generally coordinate with carboxylates to form frameworks with strong coordination bonds, according to the Pearson's hard/soft acid/base principle, where group 3 and 4 metal cations are regarded as hard acids while carboxylate ligands are hard bases. [11] One remarkable feature of MOFs with group 3 and 4 metals is that they generally can form phases containing M 6 O 8 (M = Y, Ln, An, Zr and Hf) clusters, regardless of their atomic numbers, charges and radius. This series of M 6-based MOFs is best represented by UiO series such as UiO-66 with fcu topology. [13] Under different synthetic conditions, UiO-66(M, M = An, Zr and Hf) constructed from [M 6 (μ 3-O) 4 (μ 3-OH) 4 ] clusters and linear carboxylates can be obtained, while UiO-66(M, M = Y, Ln) is assembled from Metal-organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status an...

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{Np₃₈} clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides

Cited by 36 publications

References 40 publications

Extension of the Plutonium Oxide Nanocluster Family to Include {Pu₁₆} and {Pu₂₂}

Extension of the Plutonium Oxide Nanocluster Family to Include {Pu₁₆} and {Pu₂₂}

Mononuclear to Polynuclear U^IV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation

Metal–Organic Frameworks Based on Group 3 and 4 Metals

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{Np38} clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides

Cited by 36 publications

References 40 publications

Extension of the Plutonium Oxide Nanocluster Family to Include {Pu16} and {Pu22}

Extension of the Plutonium Oxide Nanocluster Family to Include {Pu16} and {Pu22}

Mononuclear to Polynuclear UIV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation

Metal–Organic Frameworks Based on Group 3 and 4 Metals

Contact Info

Product

Resources

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{Np₃₈} clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides

Extension of the Plutonium Oxide Nanocluster Family to Include {Pu₁₆} and {Pu₂₂}

Extension of the Plutonium Oxide Nanocluster Family to Include {Pu₁₆} and {Pu₂₂}

Mononuclear to Polynuclear U^IV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation