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Inorganics, Volume 3, Issue 3 (September 2015), Pages 309-387

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Editorial

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Open AccessEditorial Frontiers in Gold Chemistry
Inorganics 2015, 3(3), 370-373; doi:10.3390/inorganics3030370
Received: 13 August 2015 / Revised: 19 August 2015 / Accepted: 19 August 2015 / Published: 24 August 2015
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Abstract
Basic chemistry of gold tells us that it can bond to sulfur, phosphorous, nitrogen, and oxygen donor ligands. The Frontiers in Gold Chemistry Special Issue covers gold complexes bonded to the different donors and their fascinating applications. This issue covers both basic chemistry
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Basic chemistry of gold tells us that it can bond to sulfur, phosphorous, nitrogen, and oxygen donor ligands. The Frontiers in Gold Chemistry Special Issue covers gold complexes bonded to the different donors and their fascinating applications. This issue covers both basic chemistry studies of gold complexes and their contemporary applications in medicine, materials chemistry, and optical sensors. There is a strong belief that aurophilicity plays a major role in the unending applications of gold. Full article
(This article belongs to the Special Issue Frontiers in Gold Chemistry)

Research

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Open AccessCommunication Activity and Stability of the Tetramanganese Polyanion [Mn4(H2O)2(PW9O34)2]10— during Electrocatalytic Water Oxidation
Inorganics 2015, 3(3), 332-340; doi:10.3390/inorganics3030332
Received: 14 April 2015 / Revised: 16 June 2015 / Accepted: 19 June 2015 / Published: 8 July 2015
Cited by 2 | PDF Full-text (2912 KB) | HTML Full-text | XML Full-text
Abstract
In natural photosynthesis, the oxygen evolving center is a tetranuclear manganese cluster stabilized by amino acids, water molecules and counter ions. However, manganese complexes are rarely exhibiting catalytic activity in water oxidation conditions. This is also true for the family of water oxidation
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In natural photosynthesis, the oxygen evolving center is a tetranuclear manganese cluster stabilized by amino acids, water molecules and counter ions. However, manganese complexes are rarely exhibiting catalytic activity in water oxidation conditions. This is also true for the family of water oxidation catalysts (WOCs) obtained from POM chemistry. We have studied the activity of the tetranuclear manganese POM [Mn4(H2O)2(PW9O34)2]10—(Mn4), the manganese analog of the well-studied [Co4(H2O)2(PW9O34)2]10— (Co4), one of the fastest and most interesting WOC candidates discovered up to date. Our electrocatalytic experiments indicate that Mn4 is indeed an active water oxidation catalysts, although unstable. It rapidly decomposes in water oxidation conditions. Bulk water electrocatalysis shows initial activities comparable to those of the cobalt counterpart, but in this case current density decreases very rapidly to become negligible just after 30 min, with the appearance of an inactive manganese oxide layer on the electrode. Full article
(This article belongs to the Special Issue Polyoxometalates) Printed Edition available
Open AccessArticle Synthesis and Characterisation of the Europium (III) Dimolybdo-Enneatungsto-Silicate Dimer, [Eu(α-SiW9Mo2O39)2]13
Inorganics 2015, 3(3), 341-354; doi:10.3390/inorganics3030341
Received: 30 April 2015 / Revised: 16 June 2015 / Accepted: 17 June 2015 / Published: 13 July 2015
Cited by 1 | PDF Full-text (2716 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The chemistry of polyoxometalates (POMs) keeps drawing the attention of researchers, since they constitute a family of discrete molecular entities whose features may be easily modulated. Often considered soluble molecular oxide analogues, POMs possess enormous potential due to a myriad of choices concerning
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The chemistry of polyoxometalates (POMs) keeps drawing the attention of researchers, since they constitute a family of discrete molecular entities whose features may be easily modulated. Often considered soluble molecular oxide analogues, POMs possess enormous potential due to a myriad of choices concerning size, shape and chemical composition that may be tailored in order to fine-tune their physico-chemical properties. Thanks to the recent progress in single-crystal X ray diffraction, new POMs exhibiting diverse and unexpected structures have been regularly reported and described. We find it relevant to systematically analyse the different equilibria that govern the formation of POMs, in order to be able to establish reliable synthesis protocols leading to new molecules. In this context, we have been able to synthesise the Eu3+-containing silico-molybdo-tungstic dimer, [Eu(α-SiW9Mo2O39)2]13. We describe the synthesis and characterisation of this new species by several physico-chemical methods, such as single-crystal X-ray diffraction, 183W NMR and electrochemistry. Full article
(This article belongs to the Special Issue Polyoxometalates) Printed Edition available
Open AccessArticle Vanadium(V)-Substitution Reactions of Wells–Dawson-Type Polyoxometalates: From [X2M18O62]6 (X = P, As; M = Mo, W) to [X2VM17O62]7
Inorganics 2015, 3(3), 355-369; doi:10.3390/inorganics3030355
Received: 14 April 2015 / Revised: 29 May 2015 / Accepted: 25 June 2015 / Published: 14 July 2015
Cited by 4 | PDF Full-text (729 KB) | HTML Full-text | XML Full-text
Abstract
The formation processes of V(V)-substituted polyoxometalates with the Wells–Dawson-type structure were studied by cyclic voltammetry and by 31P NMR and Raman spectroscopy. Generally, the vanadium-substituted heteropolytungstates, [P2VW17O62]7 and [As2VW17O62
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The formation processes of V(V)-substituted polyoxometalates with the Wells–Dawson-type structure were studied by cyclic voltammetry and by 31P NMR and Raman spectroscopy. Generally, the vanadium-substituted heteropolytungstates, [P2VW17O62]7 and [As2VW17O62]7, were prepared by mixing equimolar amounts of the corresponding lacunary species—[P2W17O61]10 and [As2W17O61]10—and vanadate. According to the results of various measurements in the present study, the tungsten site in the framework of [P2W18O62]6 and [As2W18O62]6 without defect sites could be substituted with V(V) to form the [P2VW17O62]7 and [As2VW17O62]7, respectively. The order in which the reagents were mixed was observed to be the key factor for the formation of Dawson-type V(V)-substituted polyoxometalates. Even when the concentration of each reagent was identical, the final products differed depending on the order of their addition to the reaction mixture. Unlike Wells–Dawson-type heteropolytungstates, the molybdenum sites in the framework of [P2Mo18O62]6 and [As2Mo18O62]6 were substituted with V(V), but formed Keggin-type [PVMo11O40]4 and [AsVMo11O40]4 instead of [P2VMo17O62]7 and [As2VMo17O62]7, respectively, even though a variety of reaction conditions were used. The formation constant of the [PVMo11O40]4 and [AsVMo11O40]4 was hypothesized to be substantially greater than that of the [P2VMo17O62]7 and [As2VMo17O62]7. Full article
(This article belongs to the Special Issue Polyoxometalates) Printed Edition available
Open AccessArticle Water Oxidation by Ru-Polyoxometalate Catalysts: Overpotential Dependency on the Number and Charge of the Metal Centers
Inorganics 2015, 3(3), 374-387; doi:10.3390/inorganics3030374
Received: 15 April 2015 / Revised: 3 July 2015 / Accepted: 24 July 2015 / Published: 2 September 2015
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Abstract
Water oxidation is efficiently catalyzed by several Ru-based polyoxometalate (POM) molecular catalysts differing in the number, local atomistic environment and oxidation state of the Ru sites. We employ density functional theory calculations to rationalize the dependency of the reaction overpotential on the main
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Water oxidation is efficiently catalyzed by several Ru-based polyoxometalate (POM) molecular catalysts differing in the number, local atomistic environment and oxidation state of the Ru sites. We employ density functional theory calculations to rationalize the dependency of the reaction overpotential on the main structural and electronic molecular properties. In particular, we compare the thermodynamics of the water oxidation cycle for single-site Ru-POM and multiple-site Ru4-POM complexes. For the Ru-POM case, we also investigate the reaction free energy as a function of the Ru oxidation state. We find that the overpotential of these molecular catalysts is primarily determined by the oxidation state of the metal center and is minimum for Ru(IV). In solution, the number of active sites is shown to play a minor role on the reaction energetics. The results are rationalized and discussed in terms of the local structure around the active sites and of the electrostatic screening due to the molecular structure or the solvent. Full article
(This article belongs to the Special Issue Polyoxometalates) Printed Edition available

Review

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Open AccessReview Structural and Electronic Properties of Polyoxovanadoborates Containing the [V12B18O60] Core in Different Mixed Valence States
Inorganics 2015, 3(3), 309-331; doi:10.3390/inorganics3030309
Received: 15 April 2015 / Revised: 29 May 2015 / Accepted: 5 June 2015 / Published: 3 July 2015
Cited by 1 | PDF Full-text (10215 KB) | HTML Full-text | XML Full-text
Abstract
This review summarizes all published data until April 2015 related to crystalline lattices formed by the [V12B18O60] core, which generates polyanionic clusters with different degrees of protonation and mixed-valence ratios. The negative charge of this cluster is
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This review summarizes all published data until April 2015 related to crystalline lattices formed by the [V12B18O60] core, which generates polyanionic clusters with different degrees of protonation and mixed-valence ratios. The negative charge of this cluster is counterbalanced by different cations such as protonated amines, hydronium, and alkaline, and transition metal ions. The cluster is shown to form extended 1D, 2D, or 3D frameworks by forming covalent bonds or presenting hydrogen bond interactions with the present secondary cations. These cations have little influence on the solid state reflectance UV-visible spectra of the polyanionic cluster, but are shown to modify the FT-IR spectra and the magnetic behavior of the different reported species. Full article
(This article belongs to the Special Issue Polyoxometalates) Printed Edition available

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