In Situ Formation of Unprecedented Neptunium-Oxide Wheel Clusters Stabilized in a Metal–Organic Framework

Gilson, Sara E.; Szymanowski, Jennifer E. S.; White, Jacob; Ray, Debmalya; Gagliardi, Laura; Farha, Omar K.; Burns, Peter C.

doi:10.1021/jacs.9b06187

Cited by 41 publications

(31 citation statements)

References 34 publications

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“…Recent work in actinide‐based metal–organic frameworks similarly provides evidence for the directing role of organic carboxylates, with the isolation of an unprecedented An 6 (μ 3 ‐O) 2 structural unit, as opposed to the more common An 6 (OH) 4 O 4 core, stabilized within a hybrid extended network . Indeed, several unique An species that were previously absent from descriptions of actinide structural chemistry have been observed through structural characterization of actinide‐organic coordination polymers and metal–organic frameworks . Further, Mazzanti et al.…”

Section: Introductionmentioning

confidence: 98%

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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Section: Introductionmentioning

confidence: 98%

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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“…Recent developments in inorganic synthesis and increased understanding of environmental colloids have provided new opportunities to explore the chemistry of actinides at the nanoscale. [44][45][46][47][48][49][50][51][52][53] Molecular cluster chemistry of the tetravalent actinides, exemplied by a class of actinide oxo hydroxide clusters, [54][55][56][57][58][59][60][61][62][63][64][65][66] has provided valuable structural insight into the growth of bulk AnO 2 (An ¼ actinide) by the controlled hydrolysis of molecular precursors. Synthetic techniques for actinide nanoparticles have also been reported that include direct decomposition of actinide precursors into nanoparticles in aqueous solutions by irradiation, 2,8,67 sonolysis 68,69 or via hydrothermal approaches.…”

Section: Introductionmentioning

confidence: 99%

Structural properties of ultra-small thorium and uranium dioxide nanoparticles embedded in a covalent organic framework

et al. 2020

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“…Recently, Burns and co‐workers synthesized an isostructural series of Np(V) MOFs (named as NNS1–3) on the basis of an unusual wheel‐shaped node of 18 neptunyl ions ( Figure ). [ 136 ] 18 Np(V) cations are in typical (NpO 2 ) + neptunyl ions that are further coordinated by carboxylates of 12 tetratopic linkers, forming a 4,12‐c shp topology. Strong distortion in local coordination of the neptunium atoms was evidenced by the bond lengths of Np−O that lie outside the typical range for Np(V).…”

Section: Mofs Based On Ans (Group 3 Metals)mentioning

confidence: 99%

Section: Mofs Based On Ans (Group 3 Metals)mentioning

confidence: 99%

“…b) Structure of NNS1 projected in c and a direction. Green for Np, red for O, gray for C. a,b) Reproduced with permission [136]. Copyright 2019, American Chemical Society.The Ti building blocks in the newly reported MOFs were demonstrated to be Ti 3 clusters, Ti 8 O 8 clusters, Ti 12 O 15 clusters, Ti-O chains, Ti-O sheets, and single metal TiO 6 centers(Figure 9).…”

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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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In Situ Formation of Unprecedented Neptunium-Oxide Wheel Clusters Stabilized in a Metal–Organic Framework

Cited by 41 publications

References 34 publications

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

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

Structural properties of ultra-small thorium and uranium dioxide nanoparticles embedded in a covalent organic framework

Metal–Organic Frameworks Based on Group 3 and 4 Metals

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In Situ Formation of Unprecedented Neptunium-Oxide Wheel Clusters Stabilized in a Metal–Organic Framework

Cited by 41 publications

References 34 publications

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

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

Structural properties of ultra-small thorium and uranium dioxide nanoparticles embedded in a covalent organic framework

Metal–Organic Frameworks Based on Group 3 and 4 Metals

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Product

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

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