Aqueous solutions of polyoxometalates (POMs) have been shown to potential as high-capacity energy storage materials due their for multi-electron redox processes, yet the mechanism reduction and practical limits are currently unknown. Herein, we explore processes that allow highly reduced POM clusters form {MO3}y absorb y electrons in aqueous solution, focusing mechanistically on Wells-Dawson structure X6[P2W18O62], which comprises 18 metal centers can uptake up reversibly (y = 18) per...

Abstract M IV molecular oxo‐clusters (M=Zr, Hf, Ce, Th, U, Np, Pu) are prolific in bottoms‐up material design, catalysis, and elucidating reaction pathways nature synthesis. Here we introduce Ce 70 , a wheel‐shaped oxo‐cluster, [Ce (OH) 36 (O) 64 (SO 4 ) 60 (H 2 O) 10 ] 4− . crystallizes into intricate high pore volume frameworks with divalent transition metals Ce‐monomer linkers. Eight crystal‐structures feature four framework types which the ‐rings linked as propellers, offset‐stacks,...

Superatoms are nanometer-sized molecules or particles that form ordered lattices, mimicking their atomic counterparts. Hierarchical assembly of superatoms gives rise to emergent properties in lattices quantum dots, p-block clusters, and fullerenes. Here, we introduce a family uranium-oxysulfate cluster anions whose hierarchical water is controlled by two parameters: acidity the lanthanide transition-metal countercation. In acid, larger LnIII (Ln = La-Ho) link hexamer (U6) oxoclusters into...

Heterometallic CeIV/M oxo clusters are underexplored yet and can benefit from synergistic properties combining cerium other metal cations to produce efficient redox catalysts. Herein, we designed synthesized a series of new Ce12V6 with different capping ligands: Ce12V6-SO4, Ce12V6-OTs (OTs: toluenesulfonic acid), Ce12V6-NBSA (NBSA: nitrobenzenesulfonic acid). Single crystal X-ray diffraction (SCXRD) for all three structures reveals cubane core formulated [Ce12(VO)6O24]18+ on the edges cube,...

Crystallization at the solid-liquid interface is difficult to spectroscopically observe and therefore challenging understand ultimately control molecular level. The Ce70-torroid formulated [CeIV70(OH)36(O)64(SO4)60(H2O)10]4-, part of a larger emerging family MIV70-materials (M = Zr, U, Ce), presents such an opportunity. We elucidated assembly mechanisms by X-ray scattering (small-angle total scattering) solutions solids as well crystallizing identifying fragments Ce70 single-crystal...

Experimental studies involving actinide compounds are inherently limited in scope due to the radioactive nature of these elements and scarcity cost their research isotopes. Now, ∼80 years after introduction concept by Glenn Seaborg, we still only have a understanding coordination chemistry f-block metals when compared more common such as s-, p-, d-blocks. This is particularly true for transplutonium actinides (Am, Cm, Bk, etc.) whose often considered similar trivalent lanthanides-mainly...

Organic ligands with carboxylate functionalities have been shown to affect the solubility, speciation, and overall chemical behavior of tetravalent metal ions. While many reports focused on actinide complexation by relatively simple monocarboxylates such as amino acids, in this work we examined Th(IV) U(IV) 4-hydroxybenzoic acid water aim understanding impact that organic backbone has solution solid state structural chemistry thorium(IV) uranium(IV) complexes. Two compounds general formula...

ConspectusPolyoxometalates (POMs, metals = V4/5+, Nb5+, Ta5+, Mo5/6+, and W5/6+) can be described as molecular metal oxides. The V, Mo, W-POMs (classic POMs) exhibit rich structural diversity with interesting redox properties, acid catalysis, inorganic ligands, colorimetric properties behavior. Nb Ta POMs, while structurally similar, are generally stable only in base behavior is rare, they synthetically far less accessible. have been studied for well over a century, Nb-POM chemistry has...

Leveraging microgram-level techniques, we here present the first transplutonium bis-pentatungstate complex: NaCs 8 Cm(W 5 O 18 ) 2 ·14H (CmW ).

Isolating isomorphic compounds of tetravalent actinides (i.e., ThIV, UIV, NpIV, and PuIV) improve our understanding the bonding behavior across series, in addition to their relationship with transition metals (Zr Hf) lanthanides (Ce). Similarities between these are particularly illuminated hydrolysis condensation aqueous systems, leading polynuclear clusters typified by hexamer [MIV6O4(OH)4]12+ building block. Prior studies have shown predominance coexistence smaller species for ThIV...

Coordination chemistry trends across the periodic table are often difficult to probe experimentally due limitations in finding a versatile but consistent chelating platform able accommodate various elements without changing its coordination mode. Herein, we present new metal-ligand systems covering wide range of ionic radii, charges, and elements. Five different ligands derived from Keggin structure (HBW11O398-, PW11O397-, SiW11O399-, GeW11O399-, GaW11O399-) were successfully crystalized...

Two thorium(IV) compounds, [Th(H2O)4Cl4]·2(HPy·Cl) (1) and (HPy)3[Th3(H2O)2Cl10(OH)5]·4(HPy·Cl) (2) (HPy = pyridinium), were isolated from acidic aqueous solution. The compounds synthesized at room temperature subsequently characterized using single crystal X-ray diffraction along with Raman IR spectroscopies. Whereas compound 1 is built discrete mononuclear Th(H2O)4Cl4 units, 2 consists of a novel hydroxo-bridged trimeric [Th3(OH)5]7+ core. Such species are largely absent discussions Th...

Atomically precise cerium oxo clusters offer a platform to investigate structure–property relationships that are much more complex in the ill-defined bulk material dioxide. We investigated activity of MCe70 torus family (M = Cd, Ce, Co, Cu, Fe, Ni, and Zn), discrete oxysulfate-based Ce70 rings linked by monomeric cation units, for CO oxidation. CuCe70 emerged as best performing catalyst among those tested, prompting our exploration role interfacial unit on catalytic activity....

Uranium(IV) oxide clusters, colloids, and materials are designed studied for 1) nuclear applications, 2) understanding the environmental fate transport of actinides, 3) exploring complex bonding behavior open-shell f-elements. UIV -oxyhydroxsulfate clusters particularly relevant in industrial processes nature. Recent studies have shown that counter-cations to these polynuclear anions differentiate rich structural topologies solid-state. Herein, we present nine different structures with...

Isolating isostructural compounds of tetravalent metals MIV (Zr, Hf, Ce, Th, U, Pu, Np) improves our understanding metal hydrolysis and coordination behavior across the periodic table. These form polynuclear clusters typified by hexamer [MIV6O4(OH)4]12+. Exploiting ammonium MIV-sulfate (CeIV, ThIV, UIV) phase space targeting rapid crystallization, we isolate common [MIV6(OH)4(O)4]12+ but with different numbers capping sulfates water molecules for CeIV, UIV. phases allowed a direct comparison...

Deciphering the solution chemistry and speciation of actinides is inherently difficult due to radioactivity, rarity, cost constraints, especially for transplutonium elements. In this context, development new chelating platforms associated spectroscopic techniques particularly important. study, we investigate a relatively overlooked class chelators actinide binding, namely, polyoxometalates (POMs). We provide first NMR measurements on americium–POM curium–POM complexes, using one-dimensional...

Abstract M IV molecular oxo‐clusters (M=Zr, Hf, Ce, Th, U, Np, Pu) are prolific in bottoms‐up material design, catalysis, and elucidating reaction pathways nature synthesis. Here we introduce Ce 70 , a wheel‐shaped oxo‐cluster, [Ce (OH) 36 (O) 64 (SO 4 ) 60 (H 2 O) 10 ] 4− . crystallizes into intricate high pore volume frameworks with divalent transition metals Ce‐monomer linkers. Eight crystal‐structures feature four framework types which the ‐rings linked as propellers, offset‐stacks,...

Polyoxometalate (POM)-based ionic liquids, with nearly infinite compositional variations to fine-tune antimicrobial and physical properties, function as water purification filters, anticorrosion/antibacterial coatings for natural stones, self-repairing acid-resistant coatings, catalysts, electroactive, stable solvents. By combining hydrophobic quaternary ammonium cations (QACs; tetraheptylammonium trihexyltetradecylammonium) butyltin-substituted polyoxotungstates [(BuSn)3(α-SiW9O37)] via...

Crystal formation of pentasodium nonadecacesium tetracosatungstate(VI) heneikosahydrate, Na 5 Cs 19 [W 24 O 84 ]·21H 2 O, was successfully achieved by the conversion [H W 12 42 ] 10− through addition excess + . The crystal structure comprising toroidal isopolyoxidometalate is presented, as well its Raman spectrum. (H O) 21 crystallizes in rhombohedral space group R \overline{3} with an obverse centering. title compound represents a new member to isopolytungstate family mixed alkali...

Coordination chemistry trends across the periodic table are often difficult to probe experimentally due limitations in finding a versatile but consistent chelating platform that can accommodate various elements without changing its coordination mode. Herein, we present new metal/ligand systems covering wide range of ionic radii, charges, and elements. Five different ligands derived from Keggin structure (HBW

We report the synthesis and characterization (Raman, FTIR, DLS, single crystal XRD) of Cs

Crystal formation of caesium thallium chloride phospho-tungstates, Cs

Engineered DNA–metal complexes and superstructures have been shown to combine superior control of DNA helices metal–metal interactions create nanowires with unique luminescence conductivity properties. Recently, their solid-state characterization reveals polymerization the metal–DNA helices, leading a one-dimensional Ag–DNA array. Here, we investigate potential polyoxometalates (POMs) connect join disrupt dimensionality nuclearity Ag chains clusters. We used [Ag(mcytosine)2]+ (mcytosine =...