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Controlling the Ring Curvature, Solution Assembly, and Reactivity of Gigantic Molybdenum Blue Wheels.
J. Am. Chem. Soc.
PUBLISHED: 09-29-2014
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We describe the synthesis, structure, self-assembly, solution chemistry, and mass spectrometry of two new gigantic decameric molybdenum blue wheels, {Mo200Ce12} (1) and {Mo100Ce6} (2), by building block rearrangement of the tetradecameric {Mo154} framework archetype and control of the architecture's curvature in solution from the addition of Ce(III). The assembly of 1 and 2 could be directed accordingly by adjusting the ionic strength and acidity of the reaction mixture. Alternatively, the dimeric cluster {Mo200Ce12} could be transformed directly to the monomeric species {Mo100Ce6} upon addition of a potassium salt. ESI-ion mobility mass spectra were successfully obtained for both {Mo200Ce12} and {Mo100Ce6}, which is the first report in molybdenum blue chemistry thereby confirming that the gigantic clusters are stable in solution and that ion mobility measurements can be used to characterize nanoscale inorganic molecules.
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Decoupled catalytic hydrogen evolution from a molecular metal oxide redox mediator in water splitting.
Science
PUBLISHED: 09-13-2014
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The electrolysis of water using renewable energy inputs is being actively pursued as a route to sustainable hydrogen production. Here we introduce a recyclable redox mediator (silicotungstic acid) that enables the coupling of low-pressure production of oxygen via water oxidation to a separate, catalytic hydrogen production step outside the electrolyzer that requires no post-electrolysis energy input. This approach sidesteps the production of high-pressure gases inside the electrolytic cell (a major cause of membrane degradation) and essentially eliminates the hazardous issue of product gas crossover at the low current densities that characterize renewables-driven water-splitting devices. We demonstrated that a platinum-catalyzed system can produce pure hydrogen over 30 times faster than state-of-the-art proton exchange membrane electrolyzers at equivalent platinum loading.
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Controlling the minimal self assembly of "complex" polyoxometalate clusters.
J. Am. Chem. Soc.
PUBLISHED: 08-26-2014
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Despite the vast number of polyoxometalate clusters now known, an ongoing and important challenge is to understand causality in the assembly of "complex" clusters at a mechanistic level, since this is the only way the rational, targeted synthesis of new compounds will ever be achieved. Often, the complexity of the reactions themselves makes such investigations near impossible, as very small changes can often make dramatic differences. Herein, we explore a very simple [A + B] binary synthetic system that gives rise to the facile assembly of two isomeric anions, [Fe(III)(H2O)2{?-Fe(III)SiW9O34(H2O)}2](11-) (1) and [Fe(III)(H2O)2{?-Fe(III)2SiW8O33(H2O)2}{?-SiW10O35}](11-) (2), which can be formed as individual and dimeric species (3) and (4). Furthermore, the simple binary nature of this synthetic system allowed its investigation by a comprehensive time-resolved ESI-MS analysis, yielding unprecedented mechanistic information regarding the initial interactions and reorganizations of the {?-SiW10} precursor in the presence of Fe(2+).
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A versatile tripodal Cu(I) reagent for C-N bond construction via nitrene-transfer chemistry: catalytic perspectives and mechanistic insights on C-H aminations/amidinations and olefin aziridinations.
J. Am. Chem. Soc.
PUBLISHED: 08-05-2014
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A Cu(I) catalyst (1), supported by a framework of strongly basic guanidinato moieties, mediates nitrene-transfer from PhI?NR sources to a wide variety of aliphatic hydrocarbons (C-H amination or amidination in the presence of nitriles) and olefins (aziridination). Product profiles are consistent with a stepwise rather than concerted C-N bond formation. Mechanistic investigations with the aid of Hammett plots, kinetic isotope effects, labeled stereochemical probes, and radical traps and clocks allow us to conclude that carboradical intermediates play a major role and are generated by hydrogen-atom abstraction from substrate C-H bonds or initial nitrene-addition to one of the olefinic carbons. Subsequent processes include solvent-caged radical recombination to afford the major amination and aziridination products but also one-electron oxidation of diffusively free carboradicals to generate amidination products due to carbocation participation. Analyses of metal- and ligand-centered events by variable temperature electrospray mass spectrometry, cyclic voltammetry, and electron paramagnetic resonance spectroscopy, coupled with computational studies, indicate that an active, but still elusive, copper-nitrene (S = 1) intermediate initially abstracts a hydrogen atom from, or adds nitrene to, C-H and C?C bonds, respectively, followed by a spin flip and radical rebound to afford intra- and intermolecular C-N containing products.
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Polyoxometalate based open-frameworks (POM-OFs).
Chem Soc Rev
PUBLISHED: 07-10-2014
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Polyoxometalate-based open frameworks (POM-OFs) are extended architectures incorporating metal-oxide cluster units and comprise an emergent family of materials with a large diversity of topologies, structural flexibility and functionality at the nanoscale. Not only do POM-OFs present a wide range of configurable structures, but also a have a vast array of physical properties which reflect the properties of the various 'modular' molecular inputs. Here we describe the methodologies that can be used to construct POM-OF materials with important catalytic, electronic, and structural properties and discuss the advantages compared to the metal organic framework analogues. We also show that it is possible to construct POM-OF materials and design and/or fine tune their functionality by manipulating the initially generated building block libraries as well as by controlling the self-assembly towards the specific intermediate (POM) species which is the chemical and structural "information" carrier of the targeted POM-OF material.
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Design and fabrication of memory devices based on nanoscale polyoxometalate clusters.
Nature
PUBLISHED: 06-26-2014
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Flash memory devices-that is, non-volatile computer storage media that can be electrically erased and reprogrammed-are vital for portable electronics, but the scaling down of metal-oxide-semiconductor (MOS) flash memory to sizes of below ten nanometres per data cell presents challenges. Molecules have been proposed to replace MOS flash memory, but they suffer from low electrical conductivity, high resistance, low device yield, and finite thermal stability, limiting their integration into current MOS technologies. Although great advances have been made in the pursuit of molecule-based flash memory, there are a number of significant barriers to the realization of devices using conventional MOS technologies. Here we show that core-shell polyoxometalate (POM) molecules can act as candidate storage nodes for MOS flash memory. Realistic, industry-standard device simulations validate our approach at the nanometre scale, where the device performance is determined mainly by the number of molecules in the storage media and not by their position. To exploit the nature of the core-shell POM clusters, we show, at both the molecular and device level, that embedding [(Se(iv)O3)2](4-) as an oxidizable dopant in the cluster core allows the oxidation of the molecule to a [Se(v)2O6](2-) moiety containing a {Se(v)-Se(v)} bond (where curly brackets indicate a moiety, not a molecule) and reveals a new 5+ oxidation state for selenium. This new oxidation state can be observed at the device level, resulting in a new type of memory, which we call 'write-once-erase'. Taken together, these results show that POMs have the potential to be used as a realistic nanoscale flash memory. Also, the configuration of the doped POM core may lead to new types of electrical behaviour. This work suggests a route to the practical integration of configurable molecules in MOS technologies as the lithographic scales approach the molecular limit.
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Exploring the symmetry, structure, and self-assembly mechanism of a gigantic seven-fold symmetric {Pd??} wheel.
Angew. Chem. Int. Ed. Engl.
PUBLISHED: 04-23-2014
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The symmetry, structure and formation mechanism of the structurally self-complementary {Pd84} = [Pd84O42(PO4)42(CH3CO2)28](70-) wheel is explored. Not only does the symmetry give rise to a non-closest packed structure, the mechanism of the wheel formation is proposed to depend on the delicate balance between reaction conditions. We achieve the resolution of gigantic polyoxopalladate species through electrophoresis and size-exclusion chromatography, the latter has been used in conjunction with electrospray mass spectrometry to probe the formation of the ring, which was found to proceed by the stepwise aggregation of {Pd6}(-) = [Pd6O4(CH3CO2)2(PO4)3Na(6-n)H(n)](-) building blocks. Furthermore, the higher-order assembly of these clusters into hollow blackberry structures of around 50?nm has been observed using dynamic and static light scattering.
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Step-by-step covalent modification of Cr-templated Anderson-type polyoxometalates.
Dalton Trans
PUBLISHED: 04-04-2014
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A series of tripodal alcohols substituted Anderson-type polyoxometalates (POMs) including mono-substituted (compounds and ), asymmetrical bi-substituted (compound ), and symmetrical bi-substituted ones (compounds and ) have been synthesized under hydrothermal conditions using a pre-designed step-by-step strategy, and compounds , and have been fully characterized by single-crystal X-ray diffraction, ESI-MS, and elemental analysis.
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Polyoxometalate clusters integrated into peptide chains and as inorganic amino acids: solution- and solid-phase approaches.
Angew. Chem. Int. Ed. Engl.
PUBLISHED: 03-12-2014
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General synthetic methods for the grafting of peptide chains onto polyoxometalate clusters by the use of general activated precursors have been developed. Using a solution-phase approach, pre-synthesized peptides can be grafted to a metal oxide cluster to produce hybrids of unprecedented scale (up to 30 residues). An adapted solid-phase method allows the incorporation of these clusters, which may be regarded as novel hybrid unnatural amino acids, during the peptide synthesis itself. These methods may open the way for the automated synthesis of peptides and perhaps even proteins that contain "inorganic" amino acids.
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Time-resolved assembly of cluster-in-cluster {Ag??}-in-{W??} polyoxometalates under supramolecular control.
Angew. Chem. Int. Ed. Engl.
PUBLISHED: 03-02-2014
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We report the time-resolved supramolecular assembly of a series of nanoscale polyoxometalate clusters (from the same one-pot reaction) of the form: [H(10+m)Ag18Cl(Te3W38O134)2]n, where n=1 and m=0 for compound 1 (after 4?days), n=2 and m=3 for compound 2 (after 10?days), and n=? and m=5 for compound 3 (after 14?days). The reaction is based upon the self-organization of two {Te3W38} units around a single chloride template and the formation of a {Ag12} cluster, giving a {Ag12}-in-{W76} cluster-in-cluster in compound 1, which further aggregates to cluster compounds 2 and 3 by supramolecular Ag-POM interactions. The proposed mechanism for the formation of the clusters has been studied by ESI-MS. Further, control experiments demonstrate the crucial role that TeO3(2-), Cl(-), and Ag(+) play in the self-assembly of compounds 1-3.
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3D Printed High-Throughput Hydrothermal Reactionware for Discovery, Optimization, and Scale-Up.
Angew. Chem. Int. Ed. Engl.
PUBLISHED: 02-21-2014
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3D printing techniques allow the laboratory-scale design and production of reactionware tailored to specific experimental requirements. To increase the range and versatility of reactionware devices, sealed, monolithic reactors suitable for use in hydrothermal synthesis have been digitally designed and realized. The fabrication process allows the introduction of reaction mixtures directly into the reactors during the production, and also enables the manufacture of devices of varying scales and geometries unavailable in traditional equipment. The utility of these devices is shown by the use of 3D printed, high-throughput array reactors to discover two new coordination polymers, optimize the synthesis of one of these, and scale-up its synthesis using larger reactors produced on the same 3D printer. Reactors were also used to produce phase-pure samples of coordination polymers MIL-96 and HKUST-1, in yields comparable to synthesis in traditional apparatus.
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Low pH electrolytic water splitting using earth-abundant metastable catalysts that self-assemble in situ.
J. Am. Chem. Soc.
PUBLISHED: 02-18-2014
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Typical catalysts for the electrolysis of water at low pH are based on precious metals (Pt for the cathode and IrO2 or RuO2 for the anode). However, these metals are rare and expensive, and hence lower cost and more abundant catalysts are needed if electrolytically produced hydrogen is to become more widely available. Herein, we show that electrode-film formation from aqueous solutions of first row transition metal ions at pH 1.6 can be induced under the action of an appropriate cell bias and that in the case of cobalt voltages across the cell in excess of 2 V lead to the formation of a pair of catalysts that show functional stability for oxygen evolution and proton reduction for over 24 h. We show that these films are metastable and that if the circuit is opened, they redissolve into the electrolyte bath with concomitant O2 and H2 evolution, such that the overall Faradaic efficiency for charge into the system versus amounts of gases obtained approaches unity for both O2 and H2. This work highlights the ability of first row transition metals to mediate heterogeneous electrolytic water splitting in acidic media by exploiting, rather than trying to avoid, the natural propensity of the catalysts to dissolve at the low pHs used. This in turn we hope will encourage others to examine the promise of metastable electrocatalysts based on abundant elements for a range of reactions for which they have traditionally been overlooked on account of their perceived instability under the prevailing conditions.
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Assembly and core transformation properties of two tetrahedral clusters: [Fe(III)13P8W60O227(OH)15(H2O)2]30- and [Fe(III)13P8W60O224(OH)12(PO4)4]33-.
Dalton Trans
PUBLISHED: 02-12-2014
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Two nanosized 2.6 nm Fe(III) substituted polyoxotungstates [Fe(III)13P8W60O227(OH)15(H2O)2](30-) (1) and [Fe(III)13P8W60O224(OH)12(PO4)4](33-) (2) are presented herein. Both clusters are synthesized from the reactions of trilacunary polyoxotungstate precursor [?-P2W15O56](12-) and FeCl3 under strict pH control at atmospheric pressure. The compounds are fully characterised in the solid state (FTIR and single-crystal XRD, elemental and thermogravimetric analyses), solution (cyclic voltammetry and UV-Vis spectroscopy) and in the gas phase (ESI-MS). An {Fe(III)13} core is present in both clusters which can be described as Archimedean solids (truncated tetrahedron, 1; elongated cuboctahedron, 2). 1 shows iron delivery properties coupled to a K(+)-triggered transformation of the {Fe13} core to a {K?Fe12} core in solution. Cyclic voltammetry shows the presence of independent W- and Fe-centred redox processes that support the stability of the clusters in solution. ESI-MS analyses confirm further the stability of 1 and 2 in the gas phase.
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Towards imaging electron density inside metal-organic framework structures.
Chem. Commun. (Camb.)
PUBLISHED: 01-17-2014
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Herein, we present electron density maps of three MOFs with different guests or post-synthetic modifications produced using single crystal X-ray data from laboratory diffractometers. Analysis of the electron density maps reveals possible differences inside the pores indicating that this approach may be used to explore frameworks using inexpensively gained X-ray data.
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Formation, self-assembly and transformation of a transient selenotungstate building block into clusters, chains and macrocycles.
Chem. Commun. (Camb.)
PUBLISHED: 01-15-2014
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The one-pot syntheses of a series of dimeric and trimeric selenotungstates based on the [Se2W12O46](12-) unit are presented alongside the structure of the tetrameric [Se8W48O176](32-) wheel. Mass spectrometry has probed the stability of these clusters whilst their electronic structure has been contrasted to their known phosphotungstate analogues.
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Discovery of gigantic molecular nanostructures using a flow reaction array as a search engine.
Nat Commun
PUBLISHED: 01-01-2014
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The discovery of gigantic molecular nanostructures like coordination and polyoxometalate clusters is extremely time-consuming since a vast combinatorial space needs to be searched, and even a systematic and exhaustive exploration of the available synthetic parameters relies on a great deal of serendipity. Here we present a synthetic methodology that combines a flow reaction array and algorithmic control to give a chemical 'real-space' search engine leading to the discovery and isolation of a range of new molecular nanoclusters based on [Mo(2)O(2)S(2)](2+)-based building blocks with either fourfold (C4) or fivefold (C5) symmetry templates and linkers. This engine leads us to isolate six new nanoscale cluster compounds: 1, {Mo(10)(C5)}; 2, {Mo(14)(C4)4(C5)2}; 3, {Mo(60)(C4)10}; 4, {Mo(48)(C4)6}; 5, {Mo(34)(C4)4}; 6, {Mo(18)(C4)9}; in only 200 automated experiments from a parameter space spanning ~5 million possible combinations.
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A bioelectrochemical approach to characterize extracellular electron transfer by Synechocystis sp. PCC6803.
PLoS ONE
PUBLISHED: 01-01-2014
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Biophotovoltaic devices employ photosynthetic organisms at the anode of a microbial fuel cell to generate electrical power. Although a range of cyanobacteria and algae have been shown to generate photocurrent in devices of a multitude of architectures, mechanistic understanding of extracellular electron transfer by phototrophs remains minimal. Here we describe a mediatorless bioelectrochemical device to measure the electrogenic output of a planktonically grown cyanobacterium, Synechocystis sp. PCC6803. Light dependent production of current is measured, and its magnitude is shown to scale with microbial cell concentration and light intensity. Bioelectrochemical characterization of a Synechocystis mutant lacking Photosystem II demonstrates conclusively that production of the majority of photocurrent requires a functional water splitting aparatus and electrons are likely ultimately derived from water. This shows the potential of the device to rapidly and quantitatively characterize photocurrent production by genetically modified strains, an approach that can be used in future studies to delineate the mechanisms of cyanobacterial extracellular electron transport.
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Towards polyoxometalate-cluster-based nano-electronics.
Chemistry
PUBLISHED: 11-08-2013
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We explore the concept that the incorporation of polyoxometalates (POMs) into complementary metal oxide semiconductor (CMOS) technologies could offer a fundamentally better way to design and engineer new types of data storage devices, due to the enhanced electronic complementarity with SiO2 , high redox potentials, and multiple redox states accessible to polyoxometalate clusters. To explore this we constructed a custom-built simulation domain bridge. Connecting DFT, for the quantum mechanical modelling part, and mesoscopic device modelling, confirms the theoretical basis for the proposed advantages of POMs in non-volatile molecular memories (NVMM) or flash-RAM.
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A redox-triggered structural rearrangement in an iodate-templated polyoxotungstate cluster cage.
Chem. Commun. (Camb.)
PUBLISHED: 09-12-2013
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The new tungstatoiodate, ?-[H5W18O59(IO3)](6-), containing I(V)O3(-) within a {W18O54} metal oxide framework has been prepared and shown by X-ray crystallography and mass spectrometry to be derived from the fully oxidised [H3W18O56(IO6)](6-) by two-electron reduction accompanied by a redox-triggered structural rearrangement where three I-O covalent bonds are broken.
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A bio-inspired, small molecule electron-coupled-proton buffer for decoupling the half-reactions of electrolytic water splitting.
J. Am. Chem. Soc.
PUBLISHED: 09-06-2013
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Electron-coupled-proton buffers (ECPBs) allow H2 and O2 evolution to be separated from each other in time during the electrolysis of water. Natural photosynthetic systems achieve an analogous feat during water splitting and employ a range of intermediate redox mediators such as quinone derivatives to aid this process. Drawing on this natural example, we show that a low molecular weight quinone derivative is capable of decoupling H2 evolution from O2 evolution at scale during electrochemical water splitting. This work could significantly lower the cost of ECPBs, paving the way for their more widespread adoption in water splitting.
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Exploring the programmable assembly of a polyoxometalate-organic hybrid via metal ion coordination.
J. Am. Chem. Soc.
PUBLISHED: 08-29-2013
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The conformational flexibility and programmed assembly of a dumbbell-shaped polyoxometalate-organic hybrid molecule comprising two Dawson-type polyoxometalates linked by a 2,2-bipyridine unit, which can be coordinate to metal ions, in this case of Zn(2+), are described. SAXS, UV/vis, and NMR spectroscopic techniques confirm that the hybrid molecules exist as the trans dumbbell in metal-ion-free solutions and can be reversibly transformed into the cis dumbbell through coordination upon the addition of ZnCl2 into a DMSO solution containing the hybrid. Subsequent addition of EDTA reverses the switching process by extracting the Zn(2+) cations from the hybrid. During the interchange process between trans and cis dumbbells, a further reorganization of the hybrid molecules occurs through bond rotation to minimize steric clashes between the polyoxometalate subunits, in order to stabilize the corresponding dumbbell conformation. The Zn(2+)-controlled conformational transformation of the hybrid can be further utilized to manipulate the hybrids solvophobic interaction-driven self-assembly behavior in the metal-ion driven reversible formation of 140 nm sized vesicles, studied by laser light scattering techniques.
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Exploring the assembly of supramolecular polyoxometalate triangular morphologies with Johnson solid cores: [(Mn(II)(H2O)3)2(K?{?-GeW10Mn(II)2O38}3)]19-.
Inorg Chem
PUBLISHED: 07-26-2013
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A new polyoxometalate (POM) cluster compound is presented which incorporates a trimeric assembly of Keggin-type germanotungstate fragments trapping a Johnson-type solid {Mn8} core. The mixed K-Li salt of the polyanion [(Mn(II)(H2O)3)2(K?{?-GeW10Mn(II)2O38}3)](19-) was characterized in the solid state and solution. The correlation of the assembly processes and the observed architecture of the "trinity" family of POMs is discussed.
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Quick and selective synthesis of Li6[?-P2W18O62]·28H2O soluble in various organic solvents.
Dalton Trans
PUBLISHED: 07-08-2013
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Herein we report the synthesis of ?-Dawson type POM, Li6[?-P2W18O62]·28H2O, directly from the use of Li2WO4 as the tungstate source. The salt obtained was soluble not only in water but also in a range of polar and non-polar organic solvents, such as benzene.
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Assembly of thiometalate-based {Mo16 } and {Mo36 } composite clusters combining [Mo2O2S2 ](2+) cations and selenite anions.
Adv. Mater. Weinheim
PUBLISHED: 06-05-2013
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A new family of thiometalate-based composite molecular materials is synthesized and characterized. 1.6 and 1.9 nm-sized clusters are observed in the gas phase utilizing high-resolution ESI-MS. The diversity of the selenite anions as an inorganic ligand is demonstrated by the isolation of the highest nuclearity selenium-based oxothiometalate materials reported so far. The observed proton conductivity of the selenite based oxothiometalate species renders them as promising alternative materials for fuel-cell applications.
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Naphthoxanthenyl, a New Stable Phenalenyl Type Radical Stabilized by Electronic Effects.
Org. Lett.
PUBLISHED: 06-03-2013
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Naphthoxanthenyl 1 is a new stable phenalenyl-type radical. Electrochemical studies indicate that 1 has two reversible redox processes that occur on comparatively short time scales. Crystals containing 1 can be grown by electrocrystallization, suggesting that they are conductive.
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Synthesis and characterisation of a lanthanide-capped dodecavanadate cage.
Chem. Commun. (Camb.)
PUBLISHED: 03-19-2013
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The synthesis of a series of discrete lanthanide-capped polyoxovanadate cages is presented along with magnetic and electrochemical measurements which reveal a redox active dodecavanadate cluster with potential as a new functional building unit in polyoxovanadate chemistry.
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Decoupling hydrogen and oxygen evolution during electrolytic water splitting using an electron-coupled-proton buffer.
Nat Chem
PUBLISHED: 03-02-2013
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Hydrogen is essential to several key industrial processes and could play a major role as an energy carrier in a future hydrogen economy. Although the majority of the worlds hydrogen supply currently comes from the reformation of fossil fuels, its generation from water using renewables-generated power could provide a hydrogen source without increasing atmospheric CO? levels. Conventional water electrolysis produces H? and O? simultaneously, such that these gases must be generated in separate spaces to prevent their mixing. Herein, using the polyoxometalate H?PMo??O??, we introduce the concept of the electron-coupled-proton buffer (ECPB), whereby O? and H? can be produced at separate times during water electrolysis. This could have advantages in preventing gas mixing in the headspaces of high-pressure electrolysis cells, with implications for safety and electrolyser degradation. Furthermore, we demonstrate that temporally separated O? and H? production allows greater flexibility regarding the membranes and electrodes that can be used in water-splitting cells.
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Exploring the interplay between ligand derivatisation and cation type in the assembly of hybrid polyoxometalate Mn-Andersons.
Small
PUBLISHED: 02-07-2013
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Herein a library of hybrid Mn-Anderson polyoxometalates anions are presented: 1, [(MnMo6 O18 )((OCH2 )3 -C-(CH2 )7 CHCH2 )2 ](3-) ; compound 2, [(MnMo6 O18 )((OCH2 )3 C-NHCH2 C16 H9 )2 ](3-) ; compound 3, [(MnMo6 O18 )((OCH2 )3 C-(CH2 )7 CHCH2 )1 ((OCH2 )3 C-NHCH2 C16 H9 )1 ](3-) ; compound 4, [(MnMo6 O18 )((OCH2 )3 C-NHC(O)CH2 CHCH2 )2 ](3-) and compounds 5-9, [(MnMo6 O18 )((OCH2 )3 C-NHC(O)(CH2 )x CH3 )2 ]), where x = 4, 10, 12, 14, and 18 respectively. The compounds resulting from the cation exchange of the anions 1-9 to give TBA (a) and DMDOA (b) salts, and additionally for compounds 1, 2 and 3, tetraphenylphosphonium (PPh4 ) (c) salts, are explored at the air/water interface using scanning force microscopy, showing a range of architectures including hexagonal structures, nanofibers and other supramolecular forms. Additionally the solid-state structures for compounds 1c, 2c, 4a, 6a, 9a, are presented for the first time and these investigations demonstrate the delicate interplay between the structure of the covalently derivatised hybrid organo-clusters as well as the ion-exchange cation types.
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Use of ion-mobility mass spectrometry (IMS-MS) to map polyoxometalate Keplerate clusters and their supramolecular assemblies.
Chem. Commun. (Camb.)
PUBLISHED: 01-30-2013
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We present the high-resolution (HRES-MS) and ion-mobility (IMS-MS) mass spectrometry studies of icosahedral nanoscale polyoxometalate-based {L(30)}{(Mo)Mo(5)} Keplerate clusters, and demonstrate the use of IMS-MS to resolve and map intact nanoclusters, and its potential for the discovery of new structures, in this case the first gas phase observation of proto-clustering of higher order Keplerate supramolecular aggregates.
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Nanoscale control of polyoxometalate assembly: a {Mn8W4} cluster within a {W36Si4Mn10} cluster showing a new type of isomerism.
Chemistry
PUBLISHED: 01-30-2013
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Two near isomeric clusters containing a novel {Mn(8)W(4)} Keggin cluster within a [W(36)Mn(10)Si(4)O(136)(OH)(4)(H(2)O)8](24-) cluster are reported: K(10)Li(14)[W(36)Si(4)O(136)Mn(II)(10)(OH)(4)(H(2)O)(8)] (1) and K(10)Li1(3.5)Mn(0.25)[W(36)Si(4)O(136)Mn(II)(10)(OH)(4)(H(2)O)(8) ] (1). Bulk characterization of the clusters has been carried out by single crystal X-ray structure analysis, ICP-MS, TGA, ESI-MS, CV and SQUID-magnetometer analysis. X-ray analysis revealed that 1 has eight positions within the central Keggin core that were disordered W/Mn whereas 1 contained no such disorder. This subtle difference is due to a differences is how the two clusters assemble and recrystallize from the same mother liquor and represents a new type of isomerism. The rapid recrystallization process was captured via digital microscopy and this uncovered two "intermediate" types of crystal which formed temporarily and provided nucleation sites for the final clusters to assemble. The intermediates were investigated by single crystal X-ray analysis and revealed to be novel clusters K(4)Li(22)[W(36)Si(4)Mn(7)O(136)(H(2)O)(8)]·56H(2)O (2) and Mn(2)K(8)Li(14)[W(36)Si(4)Mn(7)O(136)(H(2)O)(8)]·45H(2)O (3). The intermediate clusters contained different yet related building blocks to the final clusters which allowed for the postulation of a mechanism of assembly. This demonstrates a rare example where the use X-ray crystallography directly facilitated understanding the means by which a POM assembled.
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One-pot versus sequential reactions in the self-assembly of gigantic nanoscale polyoxotungstates.
J. Am. Chem. Soc.
PUBLISHED: 01-24-2013
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By using a new type of lacunary tungstoselenite {Se(2)W(29)O(103)} (1), which contains a "defect" pentagonal {W(W)(4)} unit, we explored the assembly of clusters using this building block and demonstrate how this unit can give rise to gigantic nanomolecular species, using both a "one-pot" and "stepwise" synthetic assembly approach. Specifically, exploration of the one-pot synthetic parameter space lead to the discovery of {Co(2.5)(W(3.5)O(14))(SeW(9)O(33))(Se(2)W(30)O(107))} (2), {CoWO(H(2)O)(3)(Se(2)W(26)O(85))(Se(3)W(30)O(107))(2)} (3), and {Ni(2)W(2)O(2)Cl(H(2)O)(3)(Se(2)W(29)O(103)) (Se(3)W(30)O(107))(2)} (4), effectively demonstrating the potential of the {Se(2)W(29)} based building blocks, which was further extended by the isolation of a range of 3d transition metal doped tetramer family derivatives: {M(2)W(n)O(m)(H(2)O)(m)(Se(2)W(29)O(102))(4)} (M = Mn, Co, Ni or Zn, n = 2, m = 4; M = Cu, n = 3, m = 5) (5-9). To contrast the one-pot approach, an optimized stepwise self-assembly investigation utilizing 1 as a precursor was performed showing that the high nuclearity clusters can condense in a more controllable way allowing the tetrameric clusters (5-8) to be synthesized with higher yield, but it was also shown that 1 can be used to construct a gigantic {W(174)} hexameric-cluster {Cu(9)Cl(3)(H(2)O)(18)(Se(2)W(29)O(102))(6)} (10). Further, 1 can also dimerize to {(Se(2)W(30)O(105))(2)} (11) by addition of extra tungstate under similar conditions. All the clusters were characterized by single-crystal X-ray crystallography, chemical analysis, infrared spectroscopy, thermogravimetric analysis, and electrospray ionization mass spectrometry, which remarkably showed that all the clusters, even the largest cluster, 10 (?50 kD), could be observed as the intact cluster demonstrating the extraordinary potential of this approach to construct robust gigantic nanoscale polyoxotungstates.
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The use and misuse of photosynthesis in the quest for novel methods to harness solar energy to make fuel.
Philos Trans A Math Phys Eng Sci
PUBLISHED: 01-01-2013
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This short review will illustrate that photosynthesis can provide a real contribution towards our sustain- able, green fuel requirements in the future. However, it is argued that the focus on biofuels is misplaced and that, in the longer term, investment in artificial photosynthesis will prove much more beneficial.
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Designing artificial photosynthetic devices using hybrid organic-inorganic modules based on polyoxometalates.
Philos Trans A Math Phys Eng Sci
PUBLISHED: 01-01-2013
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Artificial photosynthesis aims at capturing solar energy and using it to produce storable fuels. However, while there is reason to be optimistic that such approaches can deliver higher energy conversion efficiencies than natural photosynthetic systems, many serious challenges remain to be addressed. Perhaps chief among these is the issue of device stability. Almost all approaches to artificial photosynthesis employ easily oxidized organic molecules as light harvesters or in catalytic centres, frequently in solution with highly oxidizing species. The elephant in the room in this regard is that oxidation of these organic moieties is likely to occur at least as rapidly as oxidation of water, meaning that current device performance is severely curtailed. Herein, we discuss one possible solution to this problem: using self-assembling organic-polyoxometalate hybrid structures to produce compartments inside which the individual component reactions of photosynthesis can occur without such a high incidence of deleterious side reactions.
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Continuous parallel ESI-MS analysis of reactions carried out in a bespoke 3D printed device.
Beilstein J Nanotechnol
PUBLISHED: 01-01-2013
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Herein, we present an approach for the rapid, straightforward and economical preparation of a tailored reactor device using three-dimensional (3D) printing, which can be directly linked to a high-resolution electrospray ionisation mass spectrometer (ESI-MS) for real-time, in-line observations. To highlight the potential of the setup, supramolecular coordination chemistry was carried out in the device, with the product of the reactions being recorded continuously and in parallel by ESI-MS. Utilising in-house-programmed computer control, the reactant flow rates and order were carefully controlled and varied, with the changes in the pump inlets being mirrored by the recorded ESI-MS spectra.
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3D-printed devices for continuous-flow organic chemistry.
Beilstein J Org Chem
PUBLISHED: 01-01-2013
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We present a study in which the versatility of 3D-printing is combined with the processing advantages of flow chemistry for the synthesis of organic compounds. Robust and inexpensive 3D-printed reactionware devices are easily connected using standard fittings resulting in complex, custom-made flow systems, including multiple reactors in a series with in-line, real-time analysis using an ATR-IR flow cell. As a proof of concept, we utilized two types of organic reactions, imine syntheses and imine reductions, to show how different reactor configurations and substrates give different products.
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Exploring the rotational isomerism in non-classical Wells-Dawson anions {W18X}: a combined theoretical and mass spectrometry study.
Dalton Trans
PUBLISHED: 12-23-2011
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We present a combined theoretical and mass spectrometry study of the rotational isomerism of the non-classical Wells-Dawson anions. The structure is larger than the Keggin anion and six geometric isomers are predicted (?, ?, ?, ?*, ?*, ?*) on the basis of structural arguments. This work explores the geometrical differences between the isomers and evaluates the stability of these unusual clusters based upon the inclusion of the different heteroatoms. We connect the theoretical results with experimental studies by exploring the fragmentation of the parent clusters by electrospray-ionisation mass spectrometry (ESI-MS). Both approaches show a general stability trend that can be postulated as follows: ?* > ?* > ?* > ? ? ? > ? where the isomers ?*, ?* and ? are the only anions of this type known to have been synthesised.
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Anion-dependent formation of helicates versus mesocates of triple-stranded M2L3 (M = Fe2+, Cu2+) complexes.
Inorg Chem
PUBLISHED: 11-30-2011
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A series of dinuclear triple-stranded complexes, [Fe(2)L(3)?X]X(6) [X = BF(4)(-) (1), ClO(4)(-) (2)], [Fe(2)L(3)?SO(4)](2)(SO(4))(5) (3), [Fe(2)L(3)?Br](BPh(4))(6) (4), Fe(2)L(3)(NO(3))Br(6) (5), and [Cu(2)L(3)?NO(3)](NO(3))(6) (6), which incorporate a central cavity to encapsulate different anions, have been synthesized via the self-assembly of iron(II) or copper(II) salts with the N,N-bis[5-(2,2-bipyridyl)methyl]imidazolium bromide (LBr) ligand. X-ray crystallographic studies (for 1-4 and 6) and elemental analyses confirmed the cagelike triple-stranded structure. The anionic guest is bound in the cage and shows remarkable influence on the outcome of the self-assembly process with regard to the configuration at the metal centers. The mesocates (with different configurations at the two metal centers) have formed in the presence of large tetrahedral anions, while helicates (with the same configuration at both metal centers) were obtained when using the relatively smaller spherical or trigonal-planar anions Br(-) or NO(3)(-).
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An unprecedented silver-decavanadate dimer investigated using ion-mobility mass spectrometry.
Chem. Commun. (Camb.)
PUBLISHED: 11-24-2011
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A silver(I)-linked decavanadate system has been synthesised, and characterised in both the solid-state and solution showing that two cluster units are held in a specific, dimeric arrangement wholly supported by cooperative hydrogen bonds, and ion-mobility mass spectrometry (IM-MS) was used to analyse the system yielding significant information on the secondary building units and aggregation behaviour supported by hydrogen bonding.
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Smart high-? nanodielectrics using solid supported polyoxometalate-rich nanostructures.
ACS Nano
PUBLISHED: 11-22-2011
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Utilizing Langmuir-Blodgett deposition and scanning probe microscopy, we have investigated the extent to which cations alter the self-assembly processes of hybrid polyoxometalates (POMs) on surfaces. The well-defined 2D hexagonal nanostructures obtained were extensively characterized and their properties were studied, and this has revealed fascinating dielectric behavior and reversible capacitive properties. The nanostructures are extremely stable under ambient conditions, and yet exhibit fascinating self-patterning upon heating. These findings present POMs as effective smart nanodielectrics and open up a new field for future POM applications.
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Connecting theory with experiment to understand the initial nucleation steps of heteropolyoxometalate clusters.
Phys Chem Chem Phys
PUBLISHED: 08-24-2011
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A complimentary combination of Density Functional Theory (DFT) methodology and Electrospray Ionization-Mass Spectrometry (ESI-MS) has been utilized to increase our limited understanding of the first nucleation steps in the formation of the [XM(12)O(40)](n-) Keggin polyoxometalates (POMs) (where addenda metal atom M = W or Mo, and the heteroatom X = P or As). We postulate that the first key steps of nucleation into discrete, high nuclearity heteropolyanions proceed via the formation of isodinuclear species (e.g. [M(2)O(7)](2-)), which undergo successive steps of protonation and water condensation to form a heterotrinuclear fragment, which acts as a template for the constituent parts required for subsequent aggregation and formation of the plenary Keggin heteropolyanion. The stability of calculated structures of the numerous postulated intermediates has been analysed and discussed in detail, and these results complemented using experimental mass spectrometry, using an assembly (reaction solution analysis) and disassembly (fragmentation of single crystals) approach. Overall, no significant differences between the Keggin POMs were found when changing the addenda metal atom (W or Mo) or the heteroatom (P or As); although small differences among the lowest-energy structures were detected.
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Exploring the structure and properties of transition metal templated {VM17(VO4)2} Dawson-like capsules.
Inorg Chem
PUBLISHED: 07-27-2011
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Vanadate(V)-templated Dawson-type capsules {V(IV)M(VI)(17)(VO(4))(2)} (M = Mo, W; 1-2) have been synthesized and investigated by electrochemical methods in aqueous and organic media using spectroscopic techniques, EPR, UV-vis/NIR, IR, and CSI-MS (cryospray ionization mass spec.), and the clusters have been examined in the solid state by magnetic studies. The collision-induced dissociation (CID-MS) studies confirmed the solution structures as well as helped pinpoint the position of the vanadium ion on the {VM(17)}-type shell, which was corroborated by EPR and theoretical studies.
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Combined theoretical and mass spectrometry study of the formation-fragmentation of small polyoxomolybdates.
Inorg Chem
PUBLISHED: 07-19-2011
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We investigate the assembly of small polyoxomolybdates using Car-Parrinello molecular dynamics simulations which show that there is an expansion of the coordination sphere of the Mo center from four to six in molybdate anions when the acidity of the solution is increased. With the help of complementary static density functional theory (DFT) calculations and electrospray ionization mass spectrometry experiments, we are able to postulate tentative mechanisms, with energy-cascade profiles, for the formation of the Lindqvist [Mo(6)O(19)](2-) anion. Similar to the family of isopolytungstates, it can be proposed that the [Mo(6)O(19)](2-) is formed by the aggregation of one molybdenum unit at a time; however, significant differences with respect to isopolytungstates are also found. The different behavior of chromates with respect to molybdates and tungstates is also considered.
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Assembly of a family of mixed metal {Mo:V} polyoxometalates templated by TeO3(2-): {Mo12V12Te3}, {Mo12V12Te2} and {Mo17V8Te}.
Chem. Commun. (Camb.)
PUBLISHED: 07-06-2011
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The influence of the pyramidal heteroanion, TeO(3)(2-) in the self-assembly of mixed metal (Mo/V) systems, is demonstrated by the isolation of three novel mixed-metal, mixed-valence architectures, {Mo(12)V(12)Te(3)} (1), {Mo(12)V(12)Te(2)} (2) and {Mo(17)V(8)Te} (3) with the tellurium centres exhibiting the novel ?(8)-TeO(4) and ?(9)-TeO(3) coordination modes while compounds 1 and 2 were discovered utilizing ESI mass spectrometry.
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Amphiphilic properties of dumbbell-shaped inorganic-organic-inorganic molecular hybrid materials in solution and at an interface.
Langmuir
PUBLISHED: 06-30-2011
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Five novel dumbbell-shaped polyoxometalate (POM)-based inorganic-organic-inorganic molecular hybrids are investigated both in polar solvents and at interfaces for potential amphiphilic properties, which are compared with those of conventional surfactants. These hybrids with the general formula {P(2)V(3)W(15)}(2)-bis(TRIS)-linker are formed by linking two Wells-Dawson-type clusters, [P(2)V(3)W(15)O(62)](9-), with different linear bis(TRIS) linker ligands between the two TRIS moieties. Laser light scattering (LLS) studies reveal the presence of self-assembled vesicular structures in water/acetone mixed solvents, and the vesicle size increases with increasing acetone content, suggesting a charge-regulated process. The elastic constants, which are used to calculate the bending energy during vesicle formation, reveal that the organic ligands play an important role in determining the self-assembly process and that the hybrids do demonstrate amphiphilic behavior at the water/air interface. Furthermore, it is shown that some of the hybrids form monolayers at the interface, with an average molecular area that can be correlated with their organic linkers, as determined from their ?-A isotherms. Finally, the hybrids not only display amphiphilic behavior akin to that of a surfactant but also exhibit an unusually high entropy contribution to vesicle formation as a result of their unique large, polar head groups, complex organic linkers, and their special molecular architectures as well as because of the involvement of the amphiphilic tetrabutylammonium (TBA) counterions.
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Hydrogen-bonded assemblies of two-electron reduced mixed-valence [XMo12O40] (X = P and Si) with p-phenylenediamines.
Inorg Chem
PUBLISHED: 06-14-2011
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Hydrogen-bonded assemblies of the two-electron reduced mixed-valence Keggin clusters [PMo(12)O(40)](5-) and [SiMo(12)O(40)](6-) were obtained by the one-pot electron-transfer reactions between p-phenylenediamine (PPD) or 2,3,5,6-tetramethyl-PPD (TMPPD) (donors) and H(+)(3)[PMo(12)O(40)](3-) or H(+)(4)[SiMo(12)O(40)](4-) (acceptors) in CH(3)CN. The redox states of the [PMo(12)O(40)](5-) and [SiMo(12)O(40)](6-) clusters were confirmed by the redox titrations and electronic absorption measurements. In (HPPD(+))(3)(H(+))(2)[PMo(12)O(40)](5-)(CH(3)CN)(3-6) (1), the N-H ~ O hydrogen-bonded interactions between the monoprotonated HPPD(+) (or diprotonated H2PPD(2+)) and the [PMo(12)O(40)](5-) resulted in a windmill-like assembly and hydrophilic one-dimensional channels are formed with a cross-sectional area of 0.065 nm(2), and these are filled by the CH(3)CN molecules. Also, the CH(3)CN molecules in salt 1 were removed by immersing the single crystals of 1 into H(2)O, CH(3)OH, and C(2)H(5)OH solvents. In the compound, (HTMPPD(+))(6)[SiMo(12)O(40)](6-)(CH(3)CN)(6) (2), the N-H ~ O hydrogen-bonded interactions between the monoprotonated HTMPPD(+) molecules and the [SiMo(12)O(40)](6-) formed a "Saturn-ring"-like assembly. Each Saturn-ring was arranged into an hexagonally packed array via hydrogen-bonded and ?-stacking interactions of HTMPPD(+), while the CH(3)CN solvent present in salt 2 are only found in the zero-dimensional isolated cavities.
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Osmotically driven crystal morphogenesis: a general approach to the fabrication of micrometer-scale tubular architectures based on polyoxometalates.
J. Am. Chem. Soc.
PUBLISHED: 03-29-2011
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The process of osmotically driven crystal morphogenesis of polyoxometalate (POM)-based crystals is investigated, whereby the transformation results in the growth of micrometer-scale tubes 10-100 ?m in diameter and many thousands of micrometers long. This process initiates when the crystals are immersed in aqueous solutions containing large cations and is governed by the solubility of the parent POM crystal. Evidence is presented that indicates the process is general to all types of POMs, with solubility of the parent crystal being the deciding parameter. A modular approach is adopted since different POM precursor crystals can form tubular architectures with a range of large cationic species, producing an ion-exchanged material that combines the large added cations and the large POM-based anions. It is also shown that the process of morphogenesis is electrostatically driven by the aggregation of anionic metal oxides with the dissolved cations. This leads to the formation of a semi-permeable membrane around the crystal. The osmotically driven ingress of water leads to an increase in pressure, and ultimately rupture of the membrane occurs, allowing a saturated solution of the POM to escape and leading to the formation of a "self-growing" microtube in the presence of the cation. It is demonstrated that the growth process is sustained by the osmotic pressure within the membrane surrounding the parent crystal, as tube growth ceases whenever this pressure is relieved. Not only is the potential of the modular approach revealed by the fact that the microtubes retain the properties of their component parts, but it is also possible to control the direction of growth and tube diameter. In addition, the solubility limits of tube growth are explored and translated into a predictive methodology for the fabrication of tubular architectures with predefined physical properties, opening the way for real applications.
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A supramolecular heteropolyoxopalladate {Pd15} cluster host encapsulating a {Pd2} dinuclear guest: [Pd(II)2?{H7Pd(II)15O10(PO4)10}](9-).
J. Am. Chem. Soc.
PUBLISHED: 03-16-2011
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A high-nuclearity polyoxopalladate compound, [Pd(II)(2)?{H(7)Pd(II)(15)O(10)(PO(4))(10)}](9-) {Pd(II)(17)}, comprising a {Pd(15)} host occupied by a {Pd(2)} guest and the parent pristine "empty" [H(7)Pd(II)(15)O(10)(P(V)O(4))(10)](13-) {Pd(15)} cluster have both been prepared and characterized by single-crystal X-ray crystallography, (31)P NMR, CSI-MS, and XPS. The encapsulated {Pd(2)} has a short Pd(II)-Pd(II) distance within the {Pd(15)} host. Solution studies indicate that the empty host and filled guest complex are in equilibrium with each other, and UV titrations revealed a binding constant of ca. 10(3) for the guest Pd(II) ions, with a binding stoichiometry of almost 2.
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Exploring the thermochromism of sulfite-embedded polyoxometalate capsules.
Phys Chem Chem Phys
PUBLISHED: 03-15-2011
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The Dawson-type polyanion [?-Mo(18)O(54)(SO(3))(2)](4-), with two SO(3)(2-) templates embedded inside a polyoxomolybdate(vi) cage, exhibits thermochromism over an exceptionally wide temperature range (?500 K). The temperature dependence of the cluster structure, established from X-ray crystallography, IR and Raman spectroscopy and DFT calculations, is related to a decreasing HOMO-LUMO gap in the near UV with increasing temperature. We postulate this is due to geometrical changes that affect both the occupied and unoccupied frontier molecular orbitals of this cluster anion.
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Observation of Fe(V)=O using variable-temperature mass spectrometry and its enzyme-like C-H and C=C oxidation reactions.
Nat Chem
PUBLISHED: 02-16-2011
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Oxo-transfer chemistry mediated by iron underpins many biological processes and today is emerging as synthetically very important for the catalytic oxidation of C-H and C=C moieties that are hard to activate conventionally. Despite the vast amount of research in this area, experimental characterization of the reactive species under catalytic conditions is very limited, although a Fe(V)=O moiety was postulated. Here we show, using variable-temperature mass spectrometry, the generation of a Fe(V)=O species within a synthetic non-haem complex at -40 °C and its reaction with an olefin. Also, with isotopic labelling we were able both to follow oxygen-atom transfer from H(2)O(2)/H(2)O through Fe(V)=O to the products and to probe the reactivity as a function of temperature. This study pioneers the implementation of variable-temperature mass spectrometry to investigate reactive intermediates.
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Nanoscale polyoxometalate-based inorganic/organic hybrids.
Chem Rec
PUBLISHED: 01-25-2011
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The latest advances in the area of polyoxometalate (POM)-based inorganic/organic hybrid materials prepared by self-assembly, covalent modification, and supramolecular interactions are presented. This Review is composed of five sections and documents the effect of organic cations on the formation of novel POMs, surfactant encapsulated POM-based hybrids, polymeric POM/organic hybrid materials, POMs-containing ionic crystals, and covalently functionalized POMs. In addition to their role in the charge-balancing, of anionic POMs, the crucial role of organic cations in the formation and functionalization of POM-based hybrid materials is discussed.
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Design and synthesis of "dumb-bell" and "triangular" inorganic-organic hybrid nanopolyoxometalate clusters and their characterisation through ESI-MS analyses.
Chemistry
PUBLISHED: 01-24-2011
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A series of tris(hydroxymethyl)aminomethane (TRIS)-based linear (bis(TRIS)) and triangular (tris(TRIS)) ligands has been synthesised and were covalently attached to the Wells-Dawson type cluster [P(2)V(3)W(15)O(62)](9-) to generate a series of nanometer-sized inorganic-organic hybrid polyoxometalate clusters. These huge hybrids, with a molecular mass similar to that of small proteins in the range of ?10-16?kDa, were unambiguously characterised by using high-resolution ESI-MS. The ESI-MS spectra of these compounds revealed, in negative ion mode, a characteristic pattern showing distinct groups of peaks corresponding to different anionic charge states ranging from 3(-) to 8(-) for the hybrids. Each peak in these individual groups could be unambiguously assigned to the corresponding hybrid cluster anion with varying combinations of tetrabutylammonium (TBA) and other cations. This study therefore highlights the prowess of the high-resolution ESI-MS for the unambiguous characterisation of large, nanoscale, inorganic-organic hybrid clusters that have huge mass, of the order of 10-16?kDa. Also, the designed synthesis of these compounds points to the fact that we were able to achieve a great deal of structural pre-design in the synthesis of these inorganic-organic hybrid polyoxometalates (POMs) by means of a ligand design route, which is often not possible in traditional "one-pot" POM synthesis.
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Electronic and photophysical properties of adducts of [Ru(bpy)3]2+ and Dawson-type sulfite polyoxomolybdates ?/?-[Mo18O54(SO3)2]4-.
Dalton Trans
PUBLISHED: 01-24-2011
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The spectroscopic and photophysical properties of [Ru(bpy)(3)](2)[[Mo(18)O(54)(SO(3))(2)], where bpy is 2,2-bipyridyl and [Mo(18)O(54)(SO(3))(2)](4-) is either the ? or ?-sulfite containing polyoxomolybdate isomer, have been measured and compared with those for the well known but structurally distinct sulfate analogue, ?-[Mo(18)O(54)(SO(4))(2)](4-). Electronic difference spectroscopy revealed the presence of new spectral features around 480 nm, although they are weak in comparison with the [Ru(bpy)(3)](2)[Mo(18)O(54)(SO(4))(2)] analogue. Surprisingly, Stern-Volmer plots of [Ru(bpy)(3)](2+) luminescence quenching by the polyoxometallate revealed the presence of both static and dynamic quenching for both ? and ?-[Mo(18)O(54)(SO(3))(2)](4-). The association constant inferred for the ion cluster [Ru(bpy)(3)](2)?-[Mo(18)O(54)(SO(4))(2)] is K = 5.9 ± 0.56 × 10(6) and that for [Ru(bpy)(3)](2)?-[Mo(18)O(54)(SO(4))(2)] is K = 1.0 ± 0.09 × 10(7). Unlike the sulfate polyoxometalates, both sulfite polyoxometalate-ruthenium adducts are non-luminescent. Despite the strong electrostatic association in the adducts resonance Raman and photoelectrochemical studies suggests that unlike the sulfato polyoxometalate analogue there is no sensitization of the polyoxometalate photochemistry by the ruthenium centre for the sulfite anions. In addition, the adducts exhibit photochemical lability in acetonitrile, attributable to decomposition of the ruthenium complex, which has not been observed for other [Ru(bpy)(3)](2+) -polyoxometalate adducts. These observations suggest that less electronic communication exists between the [Ru(bpy)(3)](2+) and the sulfite polyoxoanions relative to their sulfate polyoxoanion counterparts, despite their structural and electronic analogy. The main distinction between sulfate and sulfite polyoxometalates lies in their reversible reduction potentials, which are more positive by approximately 100 mV for the sulfite anions. This suggests that the capacity for [Ru(bpy)(3)](2+) or analogues to sensitize photoreduction in the adducts of polyoxometalates requires very sensitive redox tuning.
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Ferromagnetically coupled chiral cyanide-bridged {Ni?Fe?} cages.
Dalton Trans
PUBLISHED: 12-13-2010
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Enantiomeric, ferromagnetically coupled decanuclear {Ni?Fe?} cages with adamantane-like cores were synthesized around templating tetraethylammonium cations, as shown by crystallographic analysis and CSI-MS, and their homochiral nature was confirmed by circular dichroism measurements.
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Extended polyoxometalate framework solids: two Mn(II)-linked {P8W48} network arrays.
Inorg Chem
PUBLISHED: 11-30-2010
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Two polyoxometalate open framework (POMOF) materials have been synthesized using a secondary building unit (SBU) approach that facilitates the convergent assembly of multidimensional framework materials using a preassembled anionic SBU {P(8)W(48)}, with integrated "pore" 1 nm in diameter, and electrophilic manganese {Mn(2+)} linkers. This yields two new POMOFS with augmented hexagonal tiling (2 and 3), related to a known three-dimensional (3D) cubic array K(18)Li(6)[Mn(II)(8)(H(2)O)(48)P(8)W(48)O(184)]·108H(2)O (1), K(12)[Mn(II)(14)(H(2)O)(30)P(8)W(48)O(184)]·111H(2)O (2), and K(8)Li(4)[Mn(II)(14)(H(2)O)(26)P(8)W(48)O(184)]·105H(2)O (3). These frameworks have been crystallized from aqueous Li-buffered solutions of {P(8)W(48)} and Mn(II)(ClO(4))(2)·6H(2)O via careful control of the synthetic strategy akin to a crystal engineering approach using cation and temperature control to isolate different material architectures shown by compounds 1-3.
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Assembly of titanium embedded polyoxometalates with unprecedented structural features.
Dalton Trans
PUBLISHED: 11-05-2010
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Two titanium embedded polyoxometalates with unprecedented structural features are presented: a monotitanium containing tungstoantimonate Na(13)H(3)[TiO(SbW(9)O(33))(2)]·33 H(2)O featuring a {Ti=O}(2+) moiety (1) and a hexatitanium containing tungstoarsenate K(6)[Ti(4)(H(2)O)(10)(AsTiW(8)O(33))(2)]·30 H(2)O containing a {Ti(4)(H(2)O)(10)}(16+) moiety (2). Both compounds have been fully characterised by single crystal X-ray diffraction, elemental analysis, IR and TGA. 1 is constructed from two ?-B-{Sb(III)W(9)O(33)} fragments linked by five sodium cations and an unprecedented square pyramidal Ti(O)O(4) group with a terminal Ti=O bond, and 2 exhibits a Krebs-type structure composed of two {AsTiW(8)O(33)} fragments, where one W(VI) centre has been substituted for a Ti(IV) centre in each, fused together via a belt of four additional Ti(IV) centres. This system represents the tungsten Ti-incorporated polyoxoanion with one of the highest Ti:W ratios so far reported. Additionally, 2 could also be isolated as an n-tetrabutylammonium salt and has been further characterised by electrochemistry and electrospray ionisation (ESI) MS studies. Due to the unique nature of these systems, both have been fully investigated using DFT calculations yielding highly interesting results. Structure 1 has been optimised with five sodium atoms in the belt position, which in addition to reducing the high charge of the cluster influence a stabilisation of the antimony lone pairs. Electrostatic potential calculations highlight the high electronegativity of the terminal oxygen on the titanium centre, enhancing real potentiality as a reactive site for catalysis.
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Assembly of modular asymmetric organic-inorganic polyoxometalate hybrids into anisotropic nanostructures.
J. Am. Chem. Soc.
PUBLISHED: 10-15-2010
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Three organic-inorganic hybrid Mn-Anderson polyoxometalates (POMs), with both symmetrical and asymmetrical appended groups, have been synthesized, identified using electrospray mass spectrometry, and isolated using an approach that allows the three AA, BB, and AB compounds to be structurally characterized. Investigation of the self-assembly of the hybrids on hydrophilic surfaces reveals the formation of nanofibres with characteristics that reflect the nature of the substitution of the POM yielding a route to the programmed assembly of anisotropic hybrid nanostructures.
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Controlling transformations in the assembly of polyoxometalate clusters: {Mo11V7}, {Mo17V8} and {Mo72V30}.
Chem. Commun. (Camb.)
PUBLISHED: 10-08-2010
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The reaction of molybdate with vanadium(V) in the presence of sulfite anions is explored showing how, via cation control, stepwise assembly through the {Mo(11)V(7)} cluster yields a {M(25)} cluster-based compound, [Mo(VI)(11)V(V)(5)V(IV)(2)O(52)(?(9)-SO(3))(Mo(VI)(6)V(V)O(22))](10-) (1a), which was first discovered using cryospray mass spectrometry, whereas switching the cation away from ammonium allows the direct formation of the spherical Keplerate {Mo(72)V(30)} cluster.
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Reverse-vesicle formation of organic-inorganic polyoxometalate-containing hybrid surfactants with tunable sizes.
Chemistry
PUBLISHED: 08-21-2010
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The formation of reverse-vesicular structures of the polyoxometalate-containing hybrid surfactants [nBu(4)N](3)[MnMo(6)O(18){(OCH(2))(3)-CNHCO(CH(2))(n-2)CH(3)}(2)] (Mn-Anderson-C(n), n=6, 16) in nonpolar medium was achieved by titrating toluene into Mn-Anderson-C(n)/acetonitrile (MeCN) solution. Stepwise change of the solvent polarity induces self-association of the hydrophilic Mn-Anderson cluster on the hybrid amphiphiles. The reverse-vesicle formation was characterized by laser light scattering and further confirmed by transmission electron microscopy techniques, and the vesicle sizes increase with increasing toluene contents. The assembly process was accelerated at an elevated temperature. The length of the alkyl tails on the hybrid surfactants has a minor effect on the vesicle sizes, because the strong attraction between the polyoxometalate clusters is more dominant in the reverse-vesicle formation.
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Cations in control: crystal engineering polyoxometalate clusters using cation directed self-assembly.
Dalton Trans
PUBLISHED: 08-18-2010
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The synthetic engineering of anionic polyoxometalate (POM) clusters with predefined properties tailored to specific applications is a great challenge using routine "one-pot" POM syntheses. Under such conditions, difficulties often arise from the multitude of complex reaction pathways and self-assembly processes occurring in solution. In this respect the major role of the charge balancing cations cannot be ignored, in fact such cations are crucial, both in the assembly of the building blocks, linkage to the overall cluster, and then assembly into the bulk material. Further, the role of the cation facilitating the selective crystallization of a particular cluster type cannot be divorced from the reaction process since the crystallization process itself can help pull "virtual" building blocks into being. This perspective briefly outlines our efforts towards engineering novel POM based materials, highlighting the use of large organic cations as "Shrink-wrapping" agents to isolate new POM clusters, frameworks and cage compounds. Central to this perspective is the hypothesis that, in the case of POM cluster assembly, the mechanism and various equilibria which define the clusters can be controlled by the selective crystallisation using cation control. Consequently, this indicates that the process of crystallisation can have a profound effect on self-assembly at the molecular level. We therefore propose that the crystallization process itself may define the molecular structure of the cluster leading to the conundrum, which came first, the cluster or the crystal of the cluster?
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Self-assembly of a nanosized, saddle-shaped, solution-stable polyoxometalate anion built from pentagonal building blocks: [H34W119Se8Fe2O420]54-.
J. Am. Chem. Soc.
PUBLISHED: 08-06-2010
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Precise control of the "one-pot" reaction conditions is employed for the assembly of a nanosized 2.8 nm cluster, [H(34)W(119)Se(8)Fe(2)O(420)](54-) (1a), which is templated using eight selenite units and two iron(III) centers. Not only is this cluster characterized structurally using X-ray crystallography, it is the largest polyoxotungstate to be observed intact in solution using ESI-MS, with a molecular mass of ca. 30,000 Da.
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Understanding and mapping the assembly of a family of trimeric polyoxometalates: transition metal mediated Wells-Dawson (M18)-trimers.
Dalton Trans
PUBLISHED: 06-09-2010
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Four iso-structural triple Wells-Dawson-type phosphotungstate compounds incorporating six transition metal ion linkers are presented of the form [(M2P2W16O60)3](24-/30-), 1-4, where M = Co, Mn, Fe, Ni respectively and compounds 3 and 4 are revealed for the first time uniting a family of isostructural clusters. Further, a comparative study of the solid-state arrangements of polyoxoanions 1-4 is presented as well as an in-depth discussion of the synthetic conditions which give rise to the formation of the clusters. Each cluster subunit displays an unprecedented diequatorial substitution pattern facilitating the combination of three such units into a trimer, creating central cavities in the range 6.61-6.82 A. The solid state arrangements of polyoxoanions 1, 3 and 4 are similar, but as a result of the relevant synthetic approaches, they differ greatly from that of 2. Electrochemical analysis of the new structures is detailed revealing that polyoxoanion 4 shows potential as an electrocatalyst in the reduction of nitrites.
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Heat capacity reveals the physics of a frustrated spin tube.
Phys. Rev. Lett.
PUBLISHED: 04-12-2010
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We report on theoretical and experimental results concerning the low-temperature specific heat of the frustrated spin-tube material [(CuCl(2)tachH(3)Cl]Cl(2) (tach denotes 1,3,5-triaminocyclohexane). This substance turns out to be an unusually perfect spin-tube system which allows to study the physics of quasi-one-dimensional antiferromagnetic structures in rather general terms. An analysis of the specific-heat data demonstrates that at low enough temperatures the system exhibits a Tomonaga-Luttinger liquid behavior corresponding to an effective spin-3/2 antiferromagnetic Heisenberg chain with short-range exchange interactions. On the other hand, around 2 K the composite spin structure of the chain is revealed through a Schottky-type peak in the specific heat. We argue that the dominating contribution to the peak originates from gapped magnon-type excitations related to the internal degrees of freedom of the rung spins.
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Polyoxometalates: building blocks for functional nanoscale systems.
Angew. Chem. Int. Ed. Engl.
PUBLISHED: 02-05-2010
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Polyoxometalates (POMs) are a subset of metal oxides that represent a diverse range of molecular clusters with an almost unmatched range of physical properties and the ability to form dynamic structures that can range in size from the nano- to the micrometer scale. Herein we present the very latest developments from synthesis to structure and function of POMs. We discuss the possibilities of creating highly sophisticated functional hierarchical systems with multiple, interdependent, functionalities along with a critical analysis that allows the non-specialist to learn the salient features. We propose and present a "periodic table of polyoxometalate building blocks". We also highlight some of the current issues and challenges that need to be addressed to work towards the design of functional systems based upon POM building blocks and look ahead to possible emerging application areas.
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Face-directed self-assembly of an electronically active Archimedean polyoxometalate architecture.
Nat Chem
PUBLISHED: 01-29-2010
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The convergent assembly of metal-organic frameworks has enabled the design of porous materials using a structural building unit approach, but functional systems incorporating pre-assembled structural building unit pore openings are rare. Here, we show that the face-directed assembly of a ring-shaped macrocyclic polyoxometalate structural building unit, {P(8)W(48)O(184)}(40-) with an integrated 1-nm pore as an aperture synthon, with manganese linkers yields a vast three-dimensional extended framework architecture based on a truncated cuboctahedron. The 1-nm-diameter entrance pores of the {P(8)W(48)O(184)}(40-) structural building unit lead to approximately spherical 7.24-nm(3) cavities containing exchangeable alkali-metal cations that can be replaced by transition-metal ions through a cation exchange process. Control over this process can be exerted by either electrochemically switching the overall framework charge by manipulating the oxidation state of the manganese linker ions, or by physically gating the pores with large organic cations, thus demonstrating how metal-organic framework-like structures with integrated pores and new physical properties can be assembled.
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Cation controlled assembly and transformation of mono- and bi-sulfite templated dawson-type polyoxotungstates.
Inorg Chem
PUBLISHED: 01-22-2010
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The Dawson-like polyoxometalate clusters (TEAH)(6)[H(2)W(18)O(57)(SO(3))] (1) and (DMAH)(8)[W(18)O(56)(SO(3))(2)(H(2)O)(2)] (2) were synthesized under similar reaction conditions by employing triethanolammonium (TEAH(+)) and dimethylammonium (DMAH(+)) as cations, respectively. Crystallographic studies revealed that compound 1 has a compressed, peanut-like {W(18)} cage containing a single sufilte anion where each cage metal atom supports one terminal oxo-based ligand whereas compound 2 also has a {W(18)} cage, but four of the eighteen cage metal atoms support two terminal oxo-based ligands with two sulfite anions embedded in the cluster.
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Unveiling the transient template in the self-assembly of a molecular oxide nanowheel.
Science
PUBLISHED: 01-02-2010
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Self-assembly has proven a powerful means of preparing structurally intricate nanomaterials, but the mechanism is often masked by the common one-pot mixing procedure. We employed a flow system to study the steps underlying assembly of a previously characterized molybdenum oxide wheel 3.6 nanometers in diameter. We observed crystallization of an intermediate structure in which a central {Mo36} cluster appears to template the assembly of the surrounding {Mo150} wheel. The transient nature of the template is demonstrated by its ejection after the wheel is reduced to its final electronic state. The templates role in the self-assembly mechanism is further confirmed by the deliberate addition of the template to the reaction mixture, which greatly accelerates the assembly time of the {Mo150} wheel and increases the yield.
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Fine tuning reactivity: synthesis and isolation of 1,2,3,12b-tetrahydroimidazo[1,2-f]phenanthridines.
J. Org. Chem.
PUBLISHED: 10-08-2009
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A facile route for the synthesis and isolation of 1,2,3,12b-tetrahydroimidazo[1,2-f]phenanthridines (TIPs) has been developed. The heterocycle is a reactive intermediate in the three-step cascade synthesis of 2,3-dihydro-1H-imidazo[1,2-f]phenanthridinium cations (DIPs), a biologically active DNA intercalating framework; however, the intermediate has previously only been characterized in situ. Derivatization of the structure at the imidazo-N position controls the reactivity of the intermediate with respect to electronic potential and pK(a) allowing isolation of a selection of TIP structures. Correlations between these parameters and reaction outcome have been made, and other influences such as steric and solvent effects have also been investigated.
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Controlled polymer synthesis--from biomimicry towards synthetic biology.
Chem Soc Rev
PUBLISHED: 10-06-2009
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The controlled assembly of synthetic polymer structures is now possible with an unprecedented range of functional groups and molecular architectures. In this critical review we consider how the ability to create artificial materials over lengthscales ranging from a few nm to several microns is generating systems that not only begin to mimic those in nature but also may lead to exciting applications in synthetic biology (139 references).
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Structure, magnetism, and ionic conductivity of the gigantic {Mo176}-wheel assembly: Na15Fe3Co16[Mo176O528H3(H2O)80]Cl27 x 450 H2O.
J. Am. Chem. Soc.
PUBLISHED: 09-08-2009
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Single crystals of the nanoscale polyoxomolybdate wheel, Na(15)Fe(3)Co(16)[Mo(176)O(528)(H(2)O)(80)]Cl(27) x 450 H(2)O, was synthesized by the condensation reaction of Na(0.4)Co(0.8)[MoO(4)] x 1.5 H(2)O at low pH and in the presence of an iron-based reducing agent, and these crystals were characterized by the synchrotron-based X-ray single crystal analysis, magnetic susceptibility, and ionic conductivity measurements.
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