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...

Step by step: The combined use of ESI mass spectrometry and complementary DFT approaches allows the proposal a formation mechanism for Lindqvist anion. is based on successive aggregation steps hydrogentungstate anion as "building block" with subsequent protonation water condensation. formed after five steps. Detailed facts importance to specialist readers are published "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted...

We explore the concept that incorporation of polyoxometalates (POMs) into complementary metal oxide semiconductor (CMOS) technologies could offer a fundamentally better way to design and engineer new types data storage devices, due enhanced electronic complementarity with SiO2, high redox potentials, multiple states accessible polyoxometalate clusters. To this we constructed custom-built simulation domain bridge. Connecting DFT, for quantum mechanical modelling part, mesoscopic device...

Heteroanion (HA) moieties have a key role in templating of heteropolyoxometalate (HPA) architectures, but clusters templated by two different templates are rarely reported. Herein, we show how cross-shaped HPA-based architecture can self-sort the HA pairing guests into divacant {XYW15O54} building block, with four these block units being linked together to complete architecture. We exploited this observation incorporate well-defined positions within clusters, leading isolation collection...

Abstract The design of highly flexible framework materials requires organic linkers, whereas inorganic are more robust but inflexible. Here, by using linkable rings made up tungsten oxide (P 8 W 48 O 184 ) building blocks, we synthesized an single crystal material that can undergo at least eight different crystal-to-crystal transformations, with gigantic volume contraction and expansion changes ranging from −2,170 to +1,720 Å 3 no reduction in crystallinity. Not only does this the largest...

The reactions of [γ-SiW10O36](8-) represent one the most important synthetic gateways into a vast array polyoxotungstate chemistry. Herein, we set about exploring transformation lacunary polyoxoanion [β2-SiW11O39](8-) using high-resolution electrospray mass spectrometry, density functional theory, and molecular dynamics. We show that reaction proceeds through an unexpected {SiW9} precursor capable undertaking direct β → γ isomerization via rotational transformation. remarkably low-energy...

Abstract The construction of pure‐inorganic framework materials with well‐defined design rules and building blocks is challenging. In this work, we show how a polyoxometalate cluster an integrated pore, based on [P 8 W 48 O 184 ] 40− (abbreviated as {P }), can be self‐assembled into inorganic frameworks using silver ions, which both enable reactions the well link them together. } was found to highly reactive ions resulting in situ generation fragments, forming 9 63 235 10 66 251 compound ( 1...

The self-assembly of polyoxometalate (POM) clusters remains challenging because they heavily depend on highly sensitive synthetic conditions that produce a vast library potential building blocks and subunits such explicit control is hard. This work reports new strategies to construct compressed molybdenum blue (MB) type cluster rings with range giant MB POM {Mo54}, {Mo58}, {Mo85}, {Mo108}. These prove the limits ring structure archetype, showing it possible compress by 100 metal atoms from...

We investigate the assembly of small polyoxomolybdates using Car-Parrinello molecular dynamics simulations which show that there is an expansion coordination sphere Mo center from four to six in molybdate anions when acidity solution increased. With help complementary static density functional theory (DFT) calculations and electrospray ionization mass spectrometry experiments, we are able postulate tentative mechanisms, with energy-cascade profiles, for formation Lindqvist [Mo(6)O(19)](2-)...

The one-pot syntheses of a series dimeric and trimeric selenotungstates based on the [Se2W12O46](12-) unit are presented alongside structure tetrameric [Se8W48O176](32-) wheel. Mass spectrometry has probed stability these clusters whilst their electronic been contrasted to known phosphotungstate analogues.

Polyoxometalates (POMs) are promising candidates for molecular electronic applications because (1) they inorganic molecules, which have better CMOS compatibility compared to organic molecules; (2) easily synthesized in a one-pot reaction from metal oxides (MOx) (where the M can be, e.g., W, V, or Mo, and x is an integer between 4 7); (3) POMs self-assemble form various shapes configurations, thus chemical synthesis be tailored specific device performance; (4) redox-active with multiple...

A complimentary combination of Density Functional Theory (DFT) methodology and Electrospray Ionization-Mass Spectrometry (ESI-MS) has been utilized to increase our limited understanding the first nucleation steps in formation [XM(12)O(40)](n-) Keggin polyoxometalates (POMs) (where addenda metal atom M = W or Mo, heteroatom X P As). We postulate that key into discrete, high nuclearity heteropolyanions proceed via isodinuclear species (e.g. [M(2)O(7)](2-)), which undergo successive protonation...

Two titanium embedded polyoxometalates with unprecedented structural features are presented: a monotitanium containing tungstoantimonate Na13H3[TiO(SbW9O33)2]·33 H2O featuring {TiO}2+ moiety (1) and hexatitanium tungstoarsenate K6[Ti4(H2O)10(AsTiW8O33)2]·30 {Ti4(H2O)10}16+ (2). Both compounds have been fully characterised by single crystal X-ray diffraction, elemental analysis, IR TGA. 1 is constructed from two α-B-{SbIIIW9O33} fragments linked five sodium cations an square pyramidal Ti(O)O4...

Abstract We report the synthesis, structural, and electronic characterization of theoretically predicted, but experimentally elusive δ‐isomer Keggin polyoxometalate polyanion. A family δ‐Keggin polyoxoanions general formula, (TEA)H p Na q [H 2 M 12 (XO 4 )O 33 (TEA)]⋅ r H O where , =[2,3,8] for 1 [4,1,4] were isolated by reaction tungstate(VI) vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to surface cluster thereby stabilizing polyanionic archetype. The...

Abstract By incorporating phosphorus(III)‐based anions into a polyoxometalate cage, new type of tungsten‐based unconventional Dawson‐like cluster, [W 18 O 56 (HP III 3 ) 2 (H O) ] 8− , was isolated, in which the reaction two phosphite [HPO 2− within {W } cage could be followed spectroscopically. As well as full X‐ray crystallographic analysis, we studied reactivity cluster using both solution‐state NMR spectroscopy and mass spectrometry. These techniques show that undergoes structural...

The formation of giant polyoxometalate (POM) species is relatively underexplored, as their self-assembly process complex due to the rapid kinetics. Polyoxopalladates (POPds) are a class POMs based on Pd, largest which {Pd84}Ac wheel, and its slower kinetics mean system more amenable systematic study. Here, we show that it possible follow assembly two types Pd wheels, {Pd84}Gly smaller {Pd72}Prop, formed using glycolate propionate ligands, respectively. We analyzed {Pd72}Prop mass...

We present a combined theoretical and mass spectrometry study of the rotational isomerism non-classical Wells-Dawson anions. The structure is larger than Keggin anion six geometric isomers are predicted (α, β, γ, α*, β*, γ*) on basis structural arguments. This work explores geometrical differences between evaluates stability these unusual clusters based upon inclusion different heteroatoms. connect results with experimental studies by exploring fragmentation parent electrospray-ionisation...

Non-mixed-valent reduced polyoxometalates, namely {W18O56XO6} Dawson-like clusters (X=IVII or TeVI) with a localized redox active template have been synthesized and properties compared the pure tungsten control (that is, X=WVI). Upon one-electron reduction, electron localizes on main-group element, giving IVI TeV, respectively. These potential as new type of electron-transfer reagent. As service to our authors readers, this journal provides supporting information supplied by authors. Such...

Standard density functional theory calculations with a continuous model of solvation as well Car-Parrinello molecular dynamics simulations explicit solvent molecules are carried out to analyze the effect pH solution on coordination sphere W (VI) ion. Both methodologies agree in predicting an expansion ion upon decrease pH. Continuous models, however, unable predict stable some structural isomers hydrated hydrogentungstate anion and tungstic acid.

DFT calculations were carried out to study (183)W NMR chemical shifts in the family of Keggin anions with formula alpha-[XW(12)O(40)](q-) (X=B, Al, Si, P, Ga, Ge, As, Zn), beta- and gamma-[SiW(12)O(40)](4-) geometric isomers, derivative Dawson anion [P(2)W(18)O(62)](6-), most symmetrical Lindqvist [W(6)O(19)](2-) its [W(10)O(32)](4-). In this article, we show that geometry employed calculation polyoxotungstates is extremely important if want be quantitative. Using very large basis sets QZ4P...

Abstract The structural features and the dynamic behaviour of different possible intermediates in formation Lindqvist anion, [W 6 O 19 ] 2– , according to stoichiometries observed electrospray fragmentation experiments, were analyzed by DFT calculations. Two complementary techniques used take into account effect solvent computations: (i) continuum solvation models (ii) Car–Parrinello simulations with explicit molecules. interaction W VI ions nucleophilic water molecules expands their...