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Journal Cover Inorganics
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  This is an Open Access Journal Open Access journal
   ISSN (Online) 2304-6740
   Published by MDPI Homepage  [146 journals]
  • Inorganics, Vol. 4, Pages 20: The Viscosity and Intermolecular Interaction
           of Organic and Inorganic Hybrid Systems Composed of Chiral Schiff Base
           Ni(II), Cu(II), and Zn(II) Complexes with Long Ligands, Azobenzene, and
           PMMA

    • Authors: Hiroshi Takano, Masahiro Takase, Nobumitsu Sunaga, Maiko Ito, Takashiro Akitsu
      First page: 20
      Abstract: We have here synthesized new chiral Schiff base Ni(II), Cu(II), Zn(II) complexes (Ni, Cu, Zn) and hybrid materials with azobenzene (AZ) in polymethyl methacrylate (PMMA). Linearly polarized UV light irradiation of these hybrid materials slightly increased their optical anisotropy of AZ as well as the complexes, which were measured with polarized IR and UV-Vis spectra and discussed based on TD-DFT calculations. Non-linear concentration (viscosity) dependence of PMMA solutions about artifact peaks suggested weak intermolecular interactions due to the flexibility of complexes by inserted methylene chains. Molecular modeling indicated that large spaces around complexes in PMMA resulted in easy molecular orientation (Ni > Cu > Zn) as short-term saturation of the UV light irradiation.
      PubDate: 2016-06-27
      DOI: 10.3390/inorganics4030020
      Issue No: Vol. 4, No. 3 (2016)
       
  • Inorganics, Vol. 4, Pages 21: Silylation of Dinitrogen Catalyzed by
           Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)

    • Authors: Wojciech Dzik
      First page: 21
      Abstract: Recently, homogeneous cobalt systems were reported to catalyze the reductive silylation of dinitrogen. In this study the investigations on the silylation of dinitrogen catalyzed by CoH(PPh3)3N2 are presented. We show that in the presence of the title compound, the reaction of N2 with trimethylsilylchloride and sodium yields, on average, 6.7 equivalents of tris(trimethylsilyl)amine per Co atom in THF (tetrahydrofuran). The aim was to elucidate whether the active catalyst is: (a) the [Co(PPh3)3N2]− anion formed after two-electron reduction of the title compound; or (b) a species formed via decomposition of CoH(PPh3)3N2 in the presence of the highly reactive substrates. Time profile, and IR and EPR spectroscopic investigations show instability of the pre-catalyst under the applied conditions which suggests that the catalytically active species is formed through in situ modification of the pre-catalyst.
      PubDate: 2016-07-05
      DOI: 10.3390/inorganics4030021
      Issue No: Vol. 4, No. 3 (2016)
       
  • Inorganics, Vol. 4, Pages 22: Mesoporous C/CrN and C/VN Nanocomposites
           Obtained by One-Pot Soft-Templating Process

    • Authors: Julien Kiener, Ovidiu Ersen, Julien Parmentier
      First page: 22
      Abstract: Nanocomposites of ordered mesoporous carbon associated with chromium nitride (CrN) or vanadium nitride (VN) nanoparticles were obtained by a simple one-pot synthesis based on the solvent evaporation induced self-assembly (EISA) process using Pluronic triblock surfactant as soft-template and a phenol-based resin (resol) as carbon precursor. These nanocomposites were characterized by X-ray diffraction, nitrogen physisorption and Transmission Electron Microscopy (TEM) techniques. Electron tomography (or 3D-TEM) technique was particularly useful for providing direct insight on the internal architecture of C/CrN nanocomposite. Nanocomposites showed a very well organized hexagonal mesoporous carbon structure and a relatively high concentration of nanoparticles well distributed in the porous network. The chromium and vanadium nitrides/mesoporous carbon nanocomposites could have many potential applications in catalysis, Li-ion batteries, and supercapacitors.
      PubDate: 2016-07-15
      DOI: 10.3390/inorganics4030022
      Issue No: Vol. 4, No. 3 (2016)
       
  • Inorganics, Vol. 4, Pages 23: Anion Ordering in Bichalcogenides

    • Authors: Martin Valldor
      First page: 23
      Abstract: This review contains recent developments and new insights in the research on inorganic, crystalline compounds with two different chalcogenide ions (bichalcogenides). Anion ordering is used as a parameter to form structural dimensionalities as well as local- and global-electric polarities. The reason for the electric polarity is that, in the heterogeneous bichalcogenide lattice, the individual bond-lengths between cations and anions are different from those in a homogeneous anion lattice. It is also shown that heteroleptic tetrahedral and octahedral coordinations offer a multitude of new crystal fields and coordinations for involved cations. This coordination diversity in bichalcogenides seems to be one way to surpass electro-chemical redox potentials: three oxidation states of a single transition metal can be stabilized, e.g., Ba15V12S34O3. A new type of disproportionation, related to coordination, is presented and results from chemical pressure on the bichalcogenide lattices of (La,Ce)CrS2O, transforming doubly [CrS3/3S2/2O1/1]3− (5+1) into singly [CrS4/2S2/3]7/3− (6+0) and [CrS4/3O2/1]11/3− (4+2) coordinations. Also, magnetic anisotropy is imposed by the anion ordering in BaCoSO, where magnetic interactions via S or O occur along two different crystallographic directions. Further, the potential of the anion lattice is discussed as a parameter for future materials design.
      PubDate: 2016-07-22
      DOI: 10.3390/inorganics4030023
      Issue No: Vol. 4, No. 3 (2016)
       
  • Inorganics, Vol. 4, Pages 24: Mesoporous WN/WO3-Composite Nanosheets for
           the Chemiresistive Detection of NO2 at Room Temperature

    • Authors: Fengdong Qu, Bo He, Rohiverth Guarecuco, Minghui Yang
      First page: 24
      Abstract: Composite materials, which can optimally use the advantages of different materials, have been studied extensively. Herein, hybrid tungsten nitride and oxide (WN/WO3) composites were prepared through a simple aqueous solution route followed by nitriding in NH3, for application as novel sensing materials. We found that the introduction of WN can improve the electrical properties of the composites, thus improving the gas sensing properties of the composites when compared with bare WO3. The highest sensing response was up to 21.3 for 100 ppb NO2 with a fast response time of ~50 s at room temperature, and the low detection limit was 1.28 ppb, which is far below the level that is immediately dangerous to life or health (IDLH) values (NO2: 20 ppm) defined by the U.S. National Institute for Occupational Safety and Health (NIOSH). In addition, the composites successfully lower the optimum temperature of WO3 from 300 °C to room temperature, and the composites-based sensor presents good long-term stability for NO2 of 100 ppb. Furthermore, a possible sensing mechanism is proposed.
      PubDate: 2016-07-26
      DOI: 10.3390/inorganics4030024
      Issue No: Vol. 4, No. 3 (2016)
       
  • Inorganics, Vol. 4, Pages 25: The Trans Influence in Unsymmetrical Pincer
           Palladacycles: An Experimental and Computational Study

    • Authors: Sarote Boonseng, Gavin Roffe, Rhiannon Jones, Graham Tizzard, Simon Coles, John Spencer, Hazel Cox
      First page: 25
      Abstract: A library of unsymmetrical SCN pincer palladacycles, [ClPd{2-pyr-6-(RSCH2)C6H3}], R = Et, Pr, Ph, p-MePh, and p-MeOPh, pyr = pyridine, has been synthesized via C–H bond activation, and used, along with PCN and N’CN unsymmetrical pincer palladacycles previously synthesized by the authors, to determine the extent to which the trans influence is exhibited in unsymmetrical pincer palladacycles. The trans influence is quantified by analysis of structural changes in the X-ray crystal and density functional theory (DFT) optimized structures and a topological analysis of the electron density using quantum theory of atoms in molecules (QTAIM) to determine the strength of the Pd-donor atom interaction. It is found that the trans influence is controlled by the nature of the donor atom and although the substituents on the donor-ligand affect the Pd-donor atom interaction through the varied electronic and steric constraints, they do not influence the bonding of the ligand trans to it. The data indicate that the strength of the trans influence is P > S > N. Furthermore, the synthetic route to the family of SCN pincer palladacycles presented demonstrates the potential of late stage derivitization for the effective synthesis of ligands towards unsymmetrical pincer palladacycles.
      PubDate: 2016-08-11
      DOI: 10.3390/inorganics4030025
      Issue No: Vol. 4, No. 3 (2016)
       
  • Inorganics, Vol. 4, Pages 26: Zirconium-Catalyzed Alkene
           Hydrophosphination and Dehydrocoupling with an Air-Stable, Fluorescent
           Primary Phosphine

    • Authors: Christine Bange, Neil Mucha, Morgan Cousins, Abigail Gehsmann, Anna Singer, Taylor Truax, Lee Higham, Rory Waterman
      First page: 26
      Abstract: Zirconium-catalyzed alkene hydrophosphination and dehydrocoupling with an air-stable, fluorescent primary phosphine 8-[(4-phosphino)phenyl]-4,4-dimethyl-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene furnishes fluorescent phosphine products. Hydrophosphination of the fluorescent phosphine produces products with a complete selectivity for the secondary product. A key intermediate in catalysis, a zirconium phosphido compound, was isolated.
      PubDate: 2016-08-15
      DOI: 10.3390/inorganics4030026
      Issue No: Vol. 4, No. 3 (2016)
       
  • Inorganics, Vol. 4, Pages 27: Optical Properties of Heavily Fluorinated
           Lanthanide Tris β-Diketonate Phosphine Oxide Adducts

    • Authors: Adam Swinburne, Madeleine Langford Paden, Tsz Chan, Simon Randall, Fabrizio Ortu, Alan Kenwright, Louise Natrajan
      First page: 27
      Abstract: The construction of lanthanide(III) chelates that exhibit superior photophysical properties holds great importance in biological and materials science. One strategy to increase the luminescence properties of lanthanide(III) chelates is to hinder competitive non-radiative decay processes through perfluorination of the chelating ligands. Here, the synthesis of two families of heavily fluorinated lanthanide(III) β-diketonate complexes bearing monodentate perfluorinated tris phenyl phosphine oxide ligands have been prepared through a facile one pot reaction [Ln(hfac)3{(ArF)3PO}(H2O)] and [Ln(F7-acac)3{(ArF)3PO}2] (where Ln = Sm3+, Eu3+, Tb3+, Er3+ and Yb3+). Single crystal X-ray diffraction analysis in combination with photophysical studies have been performed to investigate the factors responsible for the differences in the luminescence lifetimes and intrinsic quantum yields of the complexes. Replacement of both bound H2O and C–H oscillators in the ligand backbone has a dramatic effect on the photophysical properties of the complexes, particularly for the near infra-red emitting ion Yb3+, where a five fold increase in luminescence lifetime and quantum yield is observed. The complexes [Sm(hfac)3{(ArF)3PO}(H2O)] (1), [Yb(hfac)3{(ArF)3PO}(H2O)] (5), [Sm(F7-acac)3{(ArF)3PO}2] (6) and [Yb(F7-acac)3{(ArF)3PO}2] (10) exhibit unusually long luminescence lifetimes and attractive intrinsic quantum yields of emission in fluid solution (ΦLn = 3.4% (1); 1.4% (10)) and in the solid state (ΦLn = 8.5% (1); 2.0% (5); 26% (6); 11% (10)), which are amongst the largest values for this class of compounds to date.
      PubDate: 2016-09-20
      DOI: 10.3390/inorganics4030027
      Issue No: Vol. 4, No. 3 (2016)
       
  • Inorganics, Vol. 4, Pages 7: Direct Control of Spin Distribution and
           Anisotropy in Cu-Dithiolene Complex Anions by Light

    • Authors: Hiroki Noma, Keishi Ohara, Toshio Naito
      First page: 7
      Abstract: Electrical and magnetic properties are dominated by the (de)localization and the anisotropy in the distribution of unpaired electrons in solids. In molecular materials, these properties have been indirectly controlled through crystal structures using various chemical modifications to affect molecular structures and arrangements. In the molecular crystals, since the energy band structures can be semi-quantitatively known using band calculations and solid state spectra, one can anticipate the (de)localization of unpaired electrons in particular bands/levels, as well as interactions with other electrons. Thus, direct control of anisotropy and localization of unpaired electrons by locating them in selected energy bands/levels would realize more efficient control of electrical and magnetic properties. In this work, it has been found that the unpaired electrons on Cu(II)-complex anions can be optically controlled to behave as anisotropically-delocalized electrons (under dark) or isotropically-localized electrons like free electrons (under UV), the latter of which has hardly been observed in the ground states of Cu(II)-complexes by any chemical modifications. Although the compounds examined in this work did not switch between conductors and magnets, these findings indicate that optical excitation in the [Cu(dmit)2]2− salts should be an effective method to control spin distribution and anisotropy.
      PubDate: 2016-03-30
      DOI: 10.3390/inorganics4020007
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 8: Hexacoordinate Silicon Compounds with a
           Dianionic Tetradentate (N,N′,N′,N)-Chelating Ligand

    • First page: 8
      Abstract: In the context of our systematic investigations of penta- and hexacoordinate silicon compounds, which included dianionic tri- (O,N,O′; O,N,N′) and tetradentate (O,N,N,O; O,N,N′,O′) chelators, we have now explored silicon coordination chemistry with a dianionic tetradentate (N,N′,N′,N) chelator. The ligand [o-phenylene-bis(pyrrole-2-carbaldimine), H2L] was obtained by condensation of o-phenylenediamine and pyrrole-2-carbaldehyde and subsequently silylated with chlorotrimethylsilane/triethylamine. Transsilylation of this ligand precursor (Me3Si)2L with chlorosilanes SiCl4, PhSiCl3, Ph2SiCl2, (Anis)2SiCl2 and (4-Me2N-C6H4)PhSiCl2 afforded the hexacoordinate Si complexes LSiCl2, LSiPhCl, LSiPh2, LSi(Anis)2 and LSiPh(4-Me2N-C6H4), respectively (Anis = anisyl = 4-methoxyphenyl). 29Si NMR spectroscopy and, for LSiPh2, LSi(Anis)2 and LSiPh(4-Me2N-C6H4), single-crystal X-ray diffraction confirm hexacoordination of the Si atoms. The molecular structures of LSiCl2 and LSiPhCl were elucidated by computational methods. Despite the two different N donor sites (pyrrole N, X-type donor; imine N, L-type donor), charge delocalization within the ligand backbone results in compounds with four similar Si–N bonds. Charge distribution within the whole molecules was analyzed by calculating the Natural Charges (NCs). Although these five compounds carry electronically different monodentate substituents, their constituents reveal rather narrow ranges of their charges (Si atoms: +2.10–+2.22; monodentate substituents: −0.54–−0.56; L2−: −1.02–−1.11).
      PubDate: 2016-04-14
      DOI: 10.3390/inorganics4020008
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 9: Synthesis and Textural Characterization of
           Mesoporous and Meso-/Macroporous Silica Monoliths Obtained by Spinodal
           Decomposition

    • First page: 9
      Abstract: Silica monoliths featuring either mesopores or flow-through macropores and mesopores in their skeleton are prepared by combining spinodal phase separation and sol-gel condensation. The macroporous network is first generated by phase separation in acidic medium in the presence of polyethyleneoxides while mesoporosity is engineered in a second step in alkaline medium, possibly in the presence of alkylammonium cations as surfactants. The mesoporous monoliths, also referred as aerogels, are obtained in the presence of alkylpolyethylene oxides in acidic medium without the use of supercritical drying. The impact of the experimental conditions on pore architecture of the monoliths regarding the shape, the ordering, the size and the connectivity of the mesopores is comprehensively discussed based on a critical appraisal of the different models used for textural analysis.
      PubDate: 2016-04-18
      DOI: 10.3390/inorganics4020009
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 10: Adsorption of Water on Two-Dimensional
           Crystals: Water/Graphene and Water/Silicatene

    • Authors: Uwe Burghaus
      First page: 10
      Abstract: The adsorption of water on solid surfaces is a scientific evergreen which again recently prompted considerable attention in the materials, nano-, and surface science communities, respectively, due to conflicting evidence presented in the most highly regarded scientific journals. This mini review is a brief and personal perspective of the current literature (and our own data) about water adsorption for two examples, namely graphene and silicatene, which are both two-dimensional (2D) crystals. Silicatene, an inorganic companion of graphene, is intriguing as it presents us with the possibility to synthesize a 2D analog to zeolites by doping this crystalline silicon film. The wettability by water and whether or not support effects of epitaxial 2D crystals are present is of concern. Regarding applications: some 2D crystals appear promising for the hydrogen evolution reaction, i.e., hydrogen generation from water; a functionalization of graphene (by oxygen/water) to graphene oxide may be interesting for metal-free catalysis; the latest highlight in this field appears to be “icephobicity”, an application related to the hydrophobicity of surfaces.
      PubDate: 2016-04-25
      DOI: 10.3390/inorganics4020010
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 11: Manganese and Iron Catalysts in Alkyd Paints
           and Coatings

    • Authors: Ronald Hage, Johannes de Boer, Karin Maaijen
      First page: 11
      Abstract: Many paint, ink and coating formulations contain alkyd-based resins which cure via autoxidation mechanisms. Whilst cobalt-soaps have been used for many decades, there is a continuing and accelerating desire by paint companies to develop alternatives for the cobalt soaps, due to likely classification as carcinogens under the REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) legislation. Alternative driers, for example manganese and iron soaps, have been applied for this purpose. However, relatively poor curing capabilities make it necessary to increase the level of metal salts to such a level that often coloring of the paint formulation occurs. More recent developments include the application of manganese and iron complexes with a variety of organic ligands. This review will discuss the chemistry of alkyd resin curing, the applications and reactions of cobalt-soaps as curing agents, and, subsequently, the paint drying aspects and mechanisms of (model) alkyd curing using manganese and iron catalysts.
      PubDate: 2016-04-29
      DOI: 10.3390/inorganics4020011
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 12: Advances in Engineered Hemoproteins that
           Promote Biocatalysis

    • Authors: Kari Stone, Syeda Ahmed
      First page: 12
      Abstract: Some hemoproteins have the structural robustness to withstand extraction of the heme cofactor and replacement with a heme analog. Recent reports have reignited interest and exploration in this field by demonstrating the versatility of these systems. Heme binding proteins can be utilized as protein scaffolds to support heme analogs that can facilitate new reactivity by noncovalent bonding at the heme-binding site utilizing the proximal ligand for support. These substituted hemoproteins have the capability to enhance catalytic reactivity and functionality comparatively to their native forms. This review will focus on progress and recent advances of artificially engineered hemoproteins utilized as a new target for the development of biocatalysts.
      PubDate: 2016-05-04
      DOI: 10.3390/inorganics4020012
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 13: Synthesis, Characterization and Applications
           in Catalysis of Polyoxometalate/Zeolite Composites

    • First page: 13
      Abstract: An overview of the synthesis, characterization and catalytic applications of polyoxometalates/zeolites composites is given. The solids obtained by direct synthesis of the polyoxometalate in the presence of the zeolite are first described with their applications in catalysis. Those obtained by a direct mixing of the two components are then reviewed. In all cases, special care is taken in the localization of the polyoxometalate, inside the zeolite crystal, in mesopores or at the external surface of the crystals, as deduced from the characterization methods.
      PubDate: 2016-05-04
      DOI: 10.3390/inorganics4020013
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 14: Naphthyl-Containing Organophosphonate
           Derivatives of Keggin-Type Polyoxotungstates

    • First page: 14
      Abstract: New organophosphonate derivatives of monovacant Keggin-type polyoxotungstates that contain naphthyl groups have been synthesized and characterized in both solid state and solution. Single-crystal structural analysis shows that two phosphonate groups occupy the vacant position of the lacunary cluster unit in the isostructural compounds [N(C4H9)4]3[H(POC11H9)2(α-HBW11O39)] (TBA-1) and [N(C4H9)4]3[H(POC11H9)2(α-SiW11O39)] (TBA-2). Liquid-solution UV–Vis transmittance and solid-state diffuse reflectance spectroscopy studies reveal the presence of a new absorption band in the visible region, the charge transfer character of which has been further confirmed by time-dependent density functional theory (TD-DFT) calculations. The latter evidence that the charge transfer process is dominated by transitions from the highest occupied molecular orbital (HOMO), localized in the aromatic ring of the organic group, to the lowest unoccupied molecular orbital (LUMO), localized in the Keggin anion. Photoluminescence studies show that the fluorescent properties of the 1-naphthylmethylphosphonate group are quenched upon its incorporation into the inorganic oxo-tungstate skeleton. The solution stability of the hybrid clusters has been evaluated by a combination of 1H-, 13C- and 31P-Nuclear Magnetic Resonance spectroscopy and Electrospray Ionization-Mass Spectrometry. The hybrid polyanion [H(POC11H9)2(α-HBW11O39)]3− (1) herein constitutes the first structurally characterized organo-p-block containing borotungstate, and hence it confirms that this strategy for the organic functionalization of polyoxometalate clusters can be applied to new platforms belonging to the family of group-13 heteropolyoxotungstates.
      PubDate: 2016-05-12
      DOI: 10.3390/inorganics4020014
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 15: β,β-Isomer of Open-Wells–Dawson
           Polyoxometalate Containing a Tetra-Iron(III) Hydroxide Cluster:
           [{Fe4(H2O)(OH)5}(β,β-Si2W18O66)]9−

    • Authors: Satoshi Matsunaga, Eriko Miyamae, Yusuke Inoue, Kenji Nomiya
      First page: 15
      Abstract: The β,β-isomer of open-Wells–Dawson polyoxometalate (POM) containing a tetra-iron(III) cluster, K9[{Fe4(H2O)(OH)5}(β,β-Si2W18O66)]·17H2O (potassium salt of β,β-Fe4-open), was synthesized by reacting Na9H[A-β-SiW9O34]·23H2O with FeCl3·6H2O at pH 3, and characterized by X-ray crystallography, FTIR, elemental analysis, TG/DTA, UV–Vis, and cyclic voltammetry. X-ray crystallography revealed that the {Fe3+4(H2O)(OH)5}7+ cluster was included in the open pocket of the β,β-type open-Wells–Dawson polyanion [β,β-Si2W18O66]16− formed by the fusion of two trilacunary β-Keggin POMs, [A-β-SiW9O34]10−, via two W–O–W bonds. The β,β-open-Wells–Dawson polyanion corresponds to an open structure of the standard γ-Wells–Dawson POM. β,β-Fe4-open is the first example of the compound containing a geometrical isomer of α,α-open-Wells–Dawson structural POM.
      PubDate: 2016-05-17
      DOI: 10.3390/inorganics4020015
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 16: Synthesis, Structure, and Characterization
           of In10-Containing Open-Wells–Dawson Polyoxometalate

    • Authors: Satoshi Matsunaga, Takuya Otaki, Yusuke Inoue, Kohei Mihara, Kenji Nomiya
      First page: 16
      Abstract: We have successfully synthesized K17{[{KIn2(μ-OH)2}(α,α-Si2W18O66)]2[In6(μ-OH)13(H2O)8]}·35H2O (potassium salt of In10-open), an open-Wells–Dawson polyoxometalate (POM) containing ten indium metal atoms. This novel compound was characterized by X-ray crystallography, 29Si NMR, FTIR, complete elemental analysis, and TG/DTA. X-ray crystallography results for {[{KIn2(μ-OH)2}(α,α-Si2W18O66)]2[In6(μ-OH)13(H2O)8]}17− (In10-open) revealed two open-Wells–Dawson units containing two In3+ ions and a K+ ion, [{KIn2(μ-OH)2}(α,α-Si2W18O66)]11−, connected by an In6-hydroxide cluster moiety, [In6(μ-OH)13(H2O)8]5+. In10-open is the first example of an open-Wells–Dawson POM containing a fifth-period element. Moreover, to the best of our knowledge, it exhibits the highest nuclearity among the indium-containing POMs reported to date.
      PubDate: 2016-05-17
      DOI: 10.3390/inorganics4020016
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 17: Olivine-Based Blended Compounds as Positive
           Electrodes for Lithium Batteries

    • Authors: Christian Julien, Alain Mauger, Julie Trottier, Karim Zaghib, Pierre Hovington, Henri Groult
      First page: 17
      Abstract: Blended cathode materials made by mixing LiFePO4 (LFP) with LiMnPO4 (LMP) or LiNi1/3Mn1/3Co1/3O2 (NMC) that exhibit either high specific energy and high rate capability were investigated. The layered blend LMP–LFP and the physically mixed blend NMC–LFP are evaluated in terms of particle morphology and electrochemical performance. Results indicate that the LMP–LFP (66:33) blend has a better discharge rate than the LiMn1−yFeyPO4 with the same composition (y = 0.33), and NMC–LFP (70:30) delivers a remarkable stable capacity over 125 cycles. Finally, in situ voltage measurement methods were applied for the evaluation of the phase evolution of blended cathodes and gradual changes in cell behavior upon cycling. We also discuss through these examples the promising development of blends as future electrodes for new generations of Li-ion batteries.
      PubDate: 2016-05-31
      DOI: 10.3390/inorganics4020017
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 18: Tetrapropylammonium Occlusion in
           Nanoaggregates of Precursor of Silicalite-1 Zeolite Studied by 1H and 13C
           NMR

    • Authors: Mohamed Haouas, David Petry, Michael Anderson, Francis Taulelle
      First page: 18
      Abstract: The dynamic behavior of tetrapropylammonium (TPA) cations in the clear precursor sols for silicalite synthesis has been investigated by 1H diffusion ordered spectroscopy (DOSY), T1, T2, and T1ρ 1H relaxation, as well as 1H→13C cross polarization (CP) nuclear magnetic resonance. The DOSY NMR experiments showed the presence of strong solute–solvent interactions in concentrated sols, which are decreasing upon dilution. Similarities in dependence of diffusion coefficients with fractional power of the viscosity constant observed for nanoparticles, TPA cations and water led to the conclusion that they aggregate as anisotropic silicate-TPA particles. Relaxation studies as well as 1H→13C CP experiments provide information on dynamic properties of ethanol, water and TPA cations, which are function of silicate aggregates. The general tendency showed that the presence of silicate as oligomers and particles decreases the relaxation times, in particular T2 and T1ρH, as a consequence of involvement of these latter in ion-pairing interactions with water-solvated TPA molecules slowing down their mobility. Furthermore, from the 1H→13C CP dynamics curve profiles a change in the CP transfer regime was observed from fast (TCH << T1ρH) for solutions without silicates to moderate (TCH~T1ρH) when silicates are interacting with the TPA cations that may reflect the occlusion of TPA into flexible silicate hydrate aggregates.
      PubDate: 2016-06-01
      DOI: 10.3390/inorganics4020018
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 19: Monoanionic Tin Oligomers Featuring Sn–Sn
           or Sn–Pb Bonds: Synthesis and Characterization of a
           Tris(Triheteroarylstannyl)Stannate and -Plumbate

    • Authors: Kornelia Zeckert
      First page: 19
      Abstract: The reaction of the lithium tris(2-pyridyl)stannate [LiSn(2-py6OtBu)3] (py6OtBu = C5H3N-6-OtBu), 1, with the element(II) amides E{N(SiMe3)2}2 (E = Sn, Pb) afforded complexes [LiE{Sn(2-py6OtBu)3}3] for E = Sn (2) and E = Pb (3), which reveal three Sn–E bonds each. Compounds 2 and 3 have been characterized by solution NMR spectroscopy and X-ray crystallographic studies. Large 1J(119Sn–119/117Sn) as well as 1J(207Pb–119/117Sn) coupling constants confirm their structural integrity in solution. However, contrary to 2, complex 3 slowly disintegrates in solution to give elemental lead and the hexaheteroarylditin [Sn(2-py6OtBu)3]2 (4).
      PubDate: 2016-06-20
      DOI: 10.3390/inorganics4020019
      Issue No: Vol. 4, No. 2 (2016)
       
  • Inorganics, Vol. 4, Pages 1: Expanding the Chemistry of Actinide
           Metallocene Bromides. Synthesis, Properties and Molecular Structures of
           the Tetravalent and Trivalent Uranium Bromide Complexes: (C5Me4R)2UBr2,
           (C5Me4R)2U(O-2,6-iPr2C6H3)(Br), and [K(THF)][(C5Me4R)2UBr2] (R = Me, Et)

    • Authors: Alejandro Lichtscheidl, Justin Pagano, Brian Scott, Andrew Nelson, Jaqueline Kiplinger
      First page: 1
      Abstract: The organometallic uranium species (C5Me4R)2UBr2 (R = Me, Et) were obtained by treating their chloride analogues (C5Me4R)2UCl2 (R = Me, Et) with Me3SiBr. Treatment of (C5Me4R)2UCl2 and (C5Me4R)2UBr2 (R = Me, Et) with K(O-2,6-iPr2C6H3) afforded the halide aryloxide mixed-ligand complexes (C5Me4R)2U(O-2,6-iPr2C6H3)(X) (R = Me, Et; X = Cl, Br). Complexes (C5Me4R)2U(O-2,6-iPr2C6H3)(Br) (R = Me, Et) can also be synthesized by treating (C5Me4R)2U(O-2,6-iPr2C6H3)(Cl) (R = Me, Et) with Me3SiBr, respectively. Reduction of (C5Me4R)2UCl2 and (C5Me4R)2UBr2 (R = Me, Et) with KC8 led to isolation of uranium(III) “ate” species [K(THF)][(C5Me5)2UX2] (X = Cl, Br) and [K(THF)0.5][(C5Me4Et)2UX2] (X = Cl, Br), which can be converted to the neutral complexes (C5Me4R)2U[N(SiMe3)2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.
      PubDate: 2016-01-06
      DOI: 10.3390/inorganics4010001
      Issue No: Vol. 4, No. 1 (2016)
       
  • Inorganics, Vol. 4, Pages 2: Tuning of Hula-Hoop Coordination Geometry in
           a Dy Dimer

    • Authors: Yan Peng, Valeriu Mereacre, Christopher Anson, Annie Powell
      First page: 2
      Abstract: The reaction of DyCl3 with hydrazone Schiff base ligands and sodium acetate in the presence of triethylamine (Et3N) as base affords two dysprosium dimers: [Dy2(HL1)2(OAc)2(EtOH)(MeOH)] (1) and [Dy2(L2)2(OAc)2(H2O)2]·2MeOH (2). The DyIII ions in complexes 1 and 2 are linked by alkoxo bridges, and display “hula hoop” coordination geometries. Consequently, these two compounds show distinct magnetic properties. Complex 1 behaves as a field-induced single molecule magnet (SMM), while typical SMM behavior was observed for complex 2. In addition, comparison of the structural parameters among similar Dy2 SMMs with hula hoop-like geometry reveals the significant role played by coordination geometry and magnetic interaction in modulating the relaxation dynamics of SMMs.
      PubDate: 2016-01-08
      DOI: 10.3390/inorganics4010002
      Issue No: Vol. 4, No. 1 (2016)
       
  • Inorganics, Vol. 4, Pages 3: Acknowledgement to Reviewers of Inorganics in
           2015

    • Authors: Inorganics Editorial Office
      First page: 3
      Abstract: The editors of Inorganics would like to express their sincere gratitude to the following reviewers for assessing manuscripts in 2015. [...]
      PubDate: 2016-01-26
      DOI: 10.3390/inorganics4010003
      Issue No: Vol. 4, No. 1 (2016)
       
  • Inorganics, Vol. 4, Pages 4: A Structural and Spectroscopic Study of the
           First Uranyl Selenocyanate, [Et4N]3[UO2(NCSe)5]

    • Authors: Stefano Nuzzo, Michelle Browne, Brendan Twamley, Michael Lyons, Robert Baker
      First page: 4
      Abstract: The first example of a uranyl selenocyanate compound is reported. The compound [Et4N]3[UO2(NCSe)5] has been synthesized and fully characterized by vibrational and multinuclear (1H, 13C{1H} and 77Se{1H}) NMR spectroscopy. The photophysical properties have also been recorded and trends in a series of uranyl pseudohalides discussed. Spectroscopic evidence shows that the U–NCSe bonding is principally ionic. An electrochemical study revealed that the reduced uranyl(V) species is unstable to disproportionation and a ligand based oxidation is also observed. The structure of [Et4N]4[UO2(NCSe)5][NCSe] is also presented and Se···H–C hydrogen bonding and Se···Se chalcogen–chalcogen interactions are seen.
      PubDate: 2016-02-16
      DOI: 10.3390/inorganics4010004
      Issue No: Vol. 4, No. 1 (2016)
       
  • Inorganics, Vol. 4, Pages 5: Formation of Micro and Mesoporous Amorphous
           Silica-Based Materials from Single Source Precursors

    • Authors: Mohd Mohd Sokri, Yusuke Daiko, Zineb Mouline, Sawao Honda, Yuji Iwamoto
      First page: 5
      Abstract: Polysilazanes functionalized with alkoxy groups were designed and synthesized as single source precursors for fabrication of micro and mesoporous amorphous silica-based materials. The pyrolytic behaviors during the polymer to ceramic conversion were studied by the simultaneous thermogravimetry-mass spectrometry (TG-MS) analysis. The porosity of the resulting ceramics was characterized by the N2 adsorption/desorption isotherm measurements. The Fourier transform infrared spectroscopy (FT-IR) and Raman spectroscopic analyses as well as elemental composition analysis were performed on the polymer-derived amorphous silica-based materials, and the role of the alkoxy group as a sacrificial template for the micro and mesopore formations was discussed from a viewpoint to establish novel micro and mesoporous structure controlling technologies through the polymer-derived ceramics (PDCs) route.
      PubDate: 2016-03-09
      DOI: 10.3390/inorganics4010005
      Issue No: Vol. 4, No. 1 (2016)
       
  • Inorganics, Vol. 4, Pages 6: A Reliable Method for the Preparation of
           Multiporous Alumina Monoliths by Ice-Templating

    • First page: 6
      Abstract: Alumina supports presenting a bimodal porosity are generally advantageous for the conversion of bulky molecules such as found in biomass, refining, and petrochemistry. However, shaping of such materials, while controlling pores size and orientation, proves to be hard. This problem can be tackled by using a simple method involving sol-gel chemistry, surfactant self-assembly, and ice-templating. Herein, a systematic study of the formulation and process parameters’ influence on the final material properties is presented. This protocol results in the repeatable preparation of centimeter-sized alumina monoliths presenting a uni-directional macroporosity and structured mesopores. These monoliths should be of particular interest in high flow rate catalytic applications.
      PubDate: 2016-03-11
      DOI: 10.3390/inorganics4010006
      Issue No: Vol. 4, No. 1 (2016)
       
 
 
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