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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  [140 journals]
  • 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

    • 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 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

    • 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)
  • Inorganics, Vol. 3, Pages 388-391: Inorganic Syntheses Assisted by
           Microwave Heating

    • Authors: Cristina Leonelli, Sridhar Komarneni
      Pages: 388 - 391
      Abstract: This Special Issue on “Inorganic Syntheses Assisted by Microwave Heating” represents one of the few fully dedicated issues on inorganic microwave synthesis published by any international scientific journal and it features five papers and one review article. [...]
      PubDate: 2015-10-16
      DOI: 10.3390/inorganics3040388
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 392-428: Catalytic Organic Transformations
           Mediated by Actinide Complexes

    • Authors: Isabell Karmel, Rami Batrice, Moris Eisen
      Pages: 392 - 428
      Abstract: This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field.
      PubDate: 2015-10-30
      DOI: 10.3390/inorganics3040392
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 429-447: New Lanthanide Alkynylamidinates and

    • Authors: Farid Sroor, Cristian Hrib, Frank Edelmann
      Pages: 429 - 447
      Abstract: This contribution reports the synthesis and structural characterization of several new lithium and lanthanide alkynylamidinate complexes. Treatment of PhC≡CLi with N,N′-diorganocarbodiimides, R–N=C=N–R (R = iPr, Cy (cyclohexyl)), in THF or diethyl ether solution afforded the lithium-propiolamidinates Li[Ph–C≡C–C(NCy)2] S (1: R = iPr, S = THF; 2: R = Cy, S = THF; 3: R = Cy, S = Et2O). Single-crystal X-ray diffraction studies of 1 and 2 showed the presence of typical ladder-type dimeric structures in the solid state. Reactions of anhydrous LnCl3 (Ln = Ce, Nd, Sm or Ho) with 2 in a 1:3 molar ratio in THF afforded a series of new homoleptic lanthanide tris(propiolamidinate) complexes, [Ph–C≡C–C(NCy)2]3Ln (4: Ln = Ce; 5: Ln = Nd; 6: Ln = Sm; 7: Ln = Ho). The products were isolated in moderate to high yields (61%–89%) as brightly colored, crystalline solids. The chloro-functional neodymium(III) bis(cyclopropylethynylamidinate) complex [{c-C3H5–C≡C–C(NiPr)2}2Ln(µ-Cl)(THF)]2 (8) was prepared from NdCl3 and two equiv. of Li[c-C3H5–C≡C–C(NiPr)2] in THF and structurally characterized. A new monomeric Ce(III)-diiminophosphinate complex, [Ph2P(NSiMe3)2]2Ce(µ-Cl)2Li(THF)2 (9), has also been synthesized in a similar manner from CeCl3 and two equiv. of Li[Ph2P(NSiMe3)2]. Structurally, this complex resembles the well-known “ate” complexes (C5Me5)2Ln(µ-Cl)2Li(THF)2. Attempts to oxidize compound 9 using trityl chloride or phenyliodine(III) dichloride did not lead to an isolable cerium(IV) species.
      PubDate: 2015-11-05
      DOI: 10.3390/inorganics3040429
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 448-466: Dinuclear Lanthanide (III) Coordination
           Polymers in a Domino Reaction

    • Authors: Edward Loukopoulos, Kieran Griffiths, Geoffrey Akien, Nikolaos Kourkoumelis, Alaa Abdul-Sada, George Kostakis
      Pages: 448 - 466
      Abstract: A systematic study was performed to further optimise the catalytic room-temperature synthesis of trans-4,5-diaminocyclopent-2-enones from 2-furaldehyde and primary or secondary amines under a non-inert atmosphere. For this purpose, a series of dinuclear lanthanide (III) coordination polymers were synthesised using a dianionic Schiff base and their catalytic activities were investigated.
      PubDate: 2015-11-06
      DOI: 10.3390/inorganics3040448
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 467-481: Luminescent Lanthanide Metal Organic
           Frameworks for cis-Selective Isoprene Polymerization Catalysis

    • Authors: Samantha Russell, Thierry Loiseau, Christophe Volkringer, Marc Visseaux
      Pages: 467 - 481
      Abstract: In this study, we are combining two areas of chemistry; solid-state coordination polymers (or Metal-Organic Framework—MOF) and polymerization catalysis. MOF compounds combining two sets of different lanthanide elements (Nd3+, Eu3+/Tb3+) were used for that purpose: the use of neodymium was required due to its well-known catalytic properties in dienes polymerization. A second lanthanide, europium or terbium, was included in the MOF structure with the aim to provide luminescent properties. Several lanthanides-based MOF meeting these criteria were prepared according to different approaches, and they were further used as catalysts for the polymerization of isoprene. Stereoregular cis-polyisoprene was received, which in some cases exhibited luminescent properties in the UV-visible range.
      PubDate: 2015-11-09
      DOI: 10.3390/inorganics3040467
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 482-499: Assessing Covalency in Cerium and
           Uranium Hexachlorides: A Correlated Wavefunction and Density Functional
           Theory Study

    • Authors: Reece Beekmeyer, Andrew Kerridge
      Pages: 482 - 499
      Abstract: The electronic structure of a series of uranium and cerium hexachlorides in a variety of oxidation states was evaluated at both the correlated wavefunction and density functional (DFT) levels of theory. Following recent experimental observations of covalency in tetravalent cerium hexachlorides, bonding character was studied using topological and integrated analysis based on the quantum theory of atoms in molecules (QTAIM). This analysis revealed that M–Cl covalency was strongly dependent on oxidation state, with greater covalency found in higher oxidation state complexes. Comparison of M–Cl delocalisation indices revealed a discrepancy between correlated wavefunction and DFT-derived values. Decomposition of these delocalisation indices demonstrated that the origin of this discrepancy lay in ungerade contributions associated with the f-manifold which we suggest is due to self-interaction error inherent to DFT-based methods. By all measures used in this study, extremely similar levels of covalency between complexes of U and Ce in the same oxidation state was found.
      PubDate: 2015-11-09
      DOI: 10.3390/inorganics3040482
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 500-510: Holmium(III) Supermesityl-Imide
           Complexes Bearing Methylaluminato/Gallato Ligands

    • Pages: 500 - 510
      Abstract: Heterobimetallic µ2-imide complexes [Ho(µ2-Nmes*){Al(CH3)4}]2 (1, supermesityl = mes* = C6H2tBu3-2,4,6) and [Ho(µ2-Nmes*){Ga(CH3)4}]2 (2) have been synthesized from homoleptic complexes Ho[M(CH3)4]3 (M = Al, Ga) via deprotonation of H2Nmes* or with K[NH(mes*)] according to a salt metathesis-protonolysis tandem reaction. Single-crystal X-ray diffraction of isostructural complexes [Ho(µ2-Nmes*){M(CH3)4}]2 (M = Al, Ga) revealed asymmetric Ho2N2 metallacycles with very short Ho–N bond lengths and secondary Ho arene interactions.
      PubDate: 2015-11-10
      DOI: 10.3390/inorganics3040500
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 511-515: The Fascination of Polyoxometalate

    • Authors: Pierre-Emmanuel Car, Greta Patzke
      Pages: 511 - 515
      Abstract: We are delighted to introduce this special issue of Inorganics. [...]
      PubDate: 2015-11-23
      DOI: 10.3390/inorganics3040511
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 516-533: Gadolinium(III)-DOTA Complex
           Functionalized with BODIPY as a Potential Bimodal Contrast Agent for MRI
           and Optical Imaging

    • Authors: Matthias Ceulemans, Koen Nuyts, Wim De Borggraeve, Tatjana Parac-Vogt
      Pages: 516 - 533
      Abstract: The synthesis and characterization of a novel gadolinium(III) DOTA complex functionalized with a boron-dipyrromethene derivative (BODIPY) is described. The assembly of the complex relies on azide diazotransfer chemistry in a copper tube flow reactor. The azide thus formed is coupled directly with an alkyne via click chemistry, resulting into a paramagnetic and luminescent gadolinium(III) complex. Luminescent data and relaxometric properties of the complex have been evaluated, suggesting the potential applicability of the complexes as a bimodal contrast agent for magnetic resonance and optical imaging. The complex displays a bright emission at 523 nm with an absorption maximum of 507 nm and high quantum yields of up to 83% in water. The proton relaxivity of the complex measured at 310 K and at frequencies of 20 and 60 MHz had the values of 3.9 and 3.6 s−1·mM−1, respectively.
      PubDate: 2015-11-25
      DOI: 10.3390/inorganics3040516
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 534-553: Synthesis and Reactivity of a
           Cerium(III) Scorpionate Complex Containing a Redox Non-Innocent
           2,2′-Bipyridine Ligand

    • Authors: Fabrizio Ortu, Hao Zhu, Marie-Emmanuelle Boulon, David Mills
      Pages: 534 - 553
      Abstract: The Ce(III) hydrotris(3,5-dimethylpyrazolyl)borate complex [Ce(TpMe2)2(κ2-dmpz)] (1) (TpMe2 = {HB(dmpz)3}−; dmpz = 3,5-dimethylpyrazolide) was isolated in fair yield from the reaction of [Ce(I)3(THF)4] with two equivalents of [K(TpMe2)] via the facile decomposition of TpMe2. [Ce(TpMe2)2(bipy)] (2) was synthesized in poor yield by the “one-pot” reaction of [Ce(I)3(THF)4], bipy (bipy = 2,2′-bipyridine), KC8 and two equivalents of [K(TpMe2)] in tetrahydrofuran (THF). The reaction of 2 with N-methylmorpholine-N-oxide produced the known decomposition product [Ce(TpMe2)(μ-BOpMe2)]2 (3) (BOpMe2 = {HBO(dmpz)2}2−) in poor yield, presumably by N–O and B–N bond cleavage of a reactive intermediate. The reaction of 2 with trimethylsilylazide gave [Ce(TpMe2)2(N3)] (4) in poor yield; the fate of bipy and the trimethylsilyl group is unknown. Complexes 1–4 were characterized by single crystal XRD, NMR and FTIR spectroscopy and elemental analysis. Complex 2 was additionally probed by UV/Vis/NIR and Electron Paramagnetic Resonance (EPR) spectroscopies, Cyclic Voltammetry (CV) and magnetometry, which together indicate a formal 4f1 Ce(III) center coordinated by a bipy·− radical anion in this system.
      PubDate: 2015-11-27
      DOI: 10.3390/inorganics3040534
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 554-572: Magnetic and Photo-Physical Properties
           of Lanthanide Dinuclear Complexes Involving the
           Acid-Tetrathiafulvalene-, Dimethyl Ester Ligand

    • Pages: 554 - 572
      Abstract: The reaction between the 4,5-bis(2-pyridyl-N-oxidemethylthio)-4′,5′-dicarboxylic acid-tetrathiafulvalene-, dimethyl ester ligand (L) and the metallo-precursors Ln(hfac)3·2H2O leads to the formation of two dinuclear complexes of formula [Ln2(hfac)6(L)]·(CH2Cl2)·(C6H14)0.5 (LnIII = DyIII (1) and YbIII (2)). The X-ray structure reveals a quite regular square anti-prism symmetry for the coordination sphere of the lanthanide ion. UV-visible absorption properties have been experimentally measured and rationalized by TD-DFT calculations. The functionalization of the tetrathiafulvalene (TTF) core by two methyl ester moieties induces the appearance of an additional absorption band in the lowest-energy region of the spectrum. The latter has been identified as a HOMO (Highest Occupied Molecular Orbital)→LUMO (Lowest Unoccupied Molecular Orbital) Intra-Ligand Charge Transfer (ILCT) transition in which the HOMO and LUMO are centred on the TTF and methyl ester groups, respectively. Irradiation at 22,222 cm−1 of this ILCT band induces an efficient sensitization of the YbIII-centred emission that can be correlated to the magnetic properties.
      PubDate: 2015-12-03
      DOI: 10.3390/inorganics3040554
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 573-588: On the Dehydrocoupling of
           Alkenylacetylenes Mediated by Various Samarocene Complexes: A Charming
           Story of Metal Cooperativity Revealing a Novel Dual Metal σ-Bond
           Metathesis Type of Mechanism (DM σ-BM)

    • Authors: Christos Kefalidis, Laurent Maron
      Pages: 573 - 588
      Abstract: The prevailing reductive chemistry of Sm(II) has been accessed and explored mostly by the use of samarocene precursors. The highly reducing character of these congeners, along with their Lewis acidity and predominantly ionic bonding, allows for the relatively facile activation of C–H bonds, as well as peculiar transformations of unsaturated substrates (e.g., C–C couplings). Among other important C–C coupling reactions, the reaction of phenylacetylene with different mono- or bimetallic samarocene complexes affords trienediyl complexes of the type {[(C5Me5)2Sm]2(µ-η2:η2-PhC4Ph)}. In contrast, when t-butylacetylene is used, uncoupled monomers of the type (C5Me5)2Sm(C≡C–tBu) were obtained. Although this type of reactivity may appear to be simple, the mechanism underlying these transformations is complex. This conclusion is drawn from the density functional theory (DFT) mechanistic studies presented herein. The operating mechanistic paths consist of: (i) the oxidation of each samarium center and the concomitant double reduction of the alkyne to afford a binuclear intermediate; (ii) the C–H scission of the acetylinic bond that lies in between the two metals; (iii) a dual metal σ-bond metathesis (DM σ-SBM) process that releases H2; and eventually (iv) the C–C coupling of the two bridged μ-alkynides to give the final bimetallic trienediyl complexes. For the latter mechanistic route, the experimentally used phenylacetylene was considered first as well as the aliphatic hex-1-yne. More interestingly, we shed light into the formation of the mono(alkynide) complex, being the final experimental product of the reaction with t-butylacetylene.
      PubDate: 2015-12-04
      DOI: 10.3390/inorganics3040573
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 589-596: Synthesis and Characterization of
           Cerium(IV) Metallocenes

    • Authors: Andrew Sutton, David Clark, Brian Scott, John Gordon
      Pages: 589 - 596
      Abstract: By applying a salt metathesis approach between Ce(OtBu3)2(NO3)2(THF)2 and the potassium salts of mono- and ditrimethylsilyl substituted cyclopentadienes, we were able to isolate two new Ce(IV) metallocenes, including to the best of our knowledge, the first structurally characterized bis-cyclopentadiene Ce(IV) compound.
      PubDate: 2015-12-11
      DOI: 10.3390/inorganics3040589
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 597-635: Molecular Pnictogen Activation by Rare
           Earth and Actinide Complexes

    • Pages: 597 - 635
      Abstract: This review covers the activation of molecular pnictogens (group 15 elements) by homogeneous rare earth and actinide complexes. All examples of molecular pnictogen activation (dinitrogen, white phosphorus, yellow arsenic) by both rare earths and actinides, to date (2015), are discussed, focusing on synthetic methodology and the structure and bonding of the resulting complexes.
      PubDate: 2015-12-21
      DOI: 10.3390/inorganics3040597
      Issue No: Vol. 3, No. 4 (2015)
  • Inorganics, Vol. 3, Pages 309-331: Structural and Electronic Properties of
           Polyoxovanadoborates Containing the [V12B18O60] Core in Different Mixed
           Valence States

    • Pages: 309 - 331
      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 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.
      PubDate: 2015-07-03
      DOI: 10.3390/inorganics3030309
      Issue No: Vol. 3, No. 3 (2015)
  • Inorganics, Vol. 3, Pages 332-340: Activity and Stability of the
           Tetramanganese Polyanion [Mn4(H2O)2(PW9O34)2]10— during
           Electrocatalytic Water Oxidation

    • Pages: 332 - 340
      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 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.
      PubDate: 2015-07-08
      DOI: 10.3390/inorganics3030332
      Issue No: Vol. 3, No. 3 (2015)
  • Inorganics, Vol. 3, Pages 341-354: Synthesis and Characterisation of the
           Europium (III) Dimolybdo-Enneatungsto-Silicate Dimer,

    • Pages: 341 - 354
      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 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.
      PubDate: 2015-07-13
      DOI: 10.3390/inorganics3030341
      Issue No: Vol. 3, No. 3 (2015)
  • Inorganics, Vol. 3, Pages 355-369: Vanadium(V)-Substitution Reactions of
           Wells–Dawson-Type Polyoxometalates: From [X2M18O62]6− (X = P,
           As; M = Mo, W) to [X2VM17O62]7−

    • Authors: Tadaharu Ueda, Yuriko Nishimoto, Rie Saito, Miho Ohnishi, Jun-ichi Nambu
      Pages: 355 - 369
      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]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−.
      PubDate: 2015-07-14
      DOI: 10.3390/inorganics3030355
      Issue No: Vol. 3, No. 3 (2015)
  • Inorganics, Vol. 3, Pages 370-373: Frontiers in Gold Chemistry

    • Authors: Ahmed Mohamed
      Pages: 370 - 373
      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 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.
      PubDate: 2015-08-24
      DOI: 10.3390/inorganics3030370
      Issue No: Vol. 3, No. 3 (2015)
  • Inorganics, Vol. 3, Pages 374-387: Water Oxidation by Ru-Polyoxometalate
           Catalysts: Overpotential Dependency on the Number and Charge of the Metal

    • Authors: Simone Piccinin, Stefano Fabris
      Pages: 374 - 387
      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 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.
      PubDate: 2015-09-02
      DOI: 10.3390/inorganics3030374
      Issue No: Vol. 3, No. 3 (2015)
  • Inorganics, Vol. 3, Pages 55-81: Turning-On of Coumarin Phosphorescence in
           Acetylacetonato Platinum Complexes of Cyclometalated Pyridyl-Substituted

    • Pages: 55 - 81
      Abstract: Two pyridine-functionalized coumarins differing with respect to the site of pyridine attachment to the coumarin dye (3 in L1 or 7 in L2) and with respect to the presence (L1) or absence (L2) of a peripheral NMe2 donor were prepared and used as cyclometalating ligands towards the Pt(acac) fragment. X-ray crystal structures of complexes 1 and 2 show strong intermolecular interactions by π-stacking and short Pt∙∙∙Pt or C-H∙∙∙O hydrogen bonding that result in the formation of sheetlike packing patterns. The NMe2 donor substituent has a profound influence on the absorption and emission properties of the free coumarin dyes; L1 emits strongly while L2 is only weakly emissive. On binding to Pt(acac) the strong fluorescence of L1 is partially quenched while coumarin phosphorescence is observed from cyclometalated L1 and L2. The ligand-centered nature of the LUMO was confirmed by IR spectroelectrochemistry while the assignment of the phosphorescence emission as ligand-based rests on the vibrational structuring, the negligible solvatochromism, the small temperature-induced Stokes shifts on cooling to 77 K, the emission lifetimes, and strong oxygen quenching. (TD-)DFT calculations confirm our experimental results and provide an assignment of the electronic transitions and the spin density distributions in the T1 state.
      PubDate: 2015-04-17
      DOI: 10.3390/inorganics3020055
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 82-100: A Heteroaromatically Functionalized

    • Authors: Merinda Healey, Stephen Best, Lars Goerigk, Chris Ritchie
      Pages: 82 - 100
      Abstract: A new heteroaromatic thiophene containing organoimido functionalized hexamolybdate has been synthesized and characterized in both solid form and solution. Structural analysis shows successful introduction of the organoimido ligand through replacement of one terminal oxo site on [Mo6O19]2− to yield the singly functionalized hexamolybdate. Spectroscopic and theoretical analysis indicates charge transfer between the inorganic and organic components, with a significantly red-shifted lowest lying transition of 399 nm vs. the parent Lindqvist ion of 325 nm. Additional characterization includes, thermal gravimetric analysis (TGA), infrared (IR), cyclic voltammetry (CV), nuclear magnetic resonance (NMR) and time-dependent density functional theory (TD-DFT) studies.
      PubDate: 2015-05-08
      DOI: 10.3390/inorganics3020082
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 101-117: Microwave-Assisted Routes for the
           Synthesis of Complex Functional Oxides

    • Pages: 101 - 117
      Abstract: The synthesis of complex functional inorganic materials, such as oxides, can be successfully performed by using microwave irradiation as the source of heat. To achieve this, different routes and set-ups can be used: microwave-assisted synthesis may proceed in the solid state or in solution, aqueous or not, and the set ups may be as simple and accessible as domestic oven or quite sophisticated laboratory equipment. An obvious advantage of this innovative methodology is the considerable reduction in time—minutes rather than hours or days—and, as a consequence, energy saving. No less important is the fact that the particle growth is inhibited and the broad variety of different microwave or microwave-assisted synthesis techniques opens up opportunities for the preparation of inorganic nanoparticles and nanostructures. In this work, various microwave synthesis techniques have been employed: solid-state microwaves, single-mode microwaves using a TE10p cavity and microwave-assisted hydrothermal synthesis. Relevant examples are presented and discussed.
      PubDate: 2015-05-12
      DOI: 10.3390/inorganics3020101
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 118-138: Five Coordinate Platinum(II) in
           [Pt(bpy)(cod)(Me)][SbF6]: A Structural and Spectroscopic Study

    • Pages: 118 - 138
      Abstract: The five coordinate organoplatinum complex [Pt(bpy)(cod)(Me)][SbF6] (cod = 1,5-cyclooctadiene, bpy = 2,2’-bipyridine) was obtained reacting [Pt(cod)(Me)Cl] with Ag[SbF6] and bpy and characterized by multiple spectroscopy (IR and NMR) and single crystal XRD. Although the application of the τ values for the discrimination between trigonal bipyramidal vs. square pyramidal coordination fails, the molecular structure can be unequivocally described as basally-distorted trigonal bipyramidal. Detailed multinuclear NMR spectroscopy in solution at ambient temperature gives strong evidence for the same structure; corresponding low-temperature measurements down to −70 °C revealed no marked dynamic processes.
      PubDate: 2015-05-13
      DOI: 10.3390/inorganics3020118
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 139-154: Gilded Hope for Medicine

    • Authors: Mohamed Naggar, Ihsan Shehadi, Hanan Abdou, Ahmed Mohamed
      Pages: 139 - 154
      Abstract: Gold is emerging as a potential therapeutic agent in the treatment of arthritis, cancer and AIDS. The therapeutic mechanism of arthritic gold drugs and their modification in the presence of stomach hydrochloric acid, in the joints, and in the presence of mild and strong oxidizing agents is a matter of debate. It is believed that gold affects the entire immune response and reduces its potency and limits its oxidizing nature. DNA apparently is not the main target of gold in cancer treatment. Rheumatoid arthritis, cancer, heart diseases and recently AIDS have all been targeted with gold nanoparticles therapy. The era of gold nanoparticles started with cancer imaging and treatment studies. Gold nanoparticles have emerged as smart drug vehicles.
      PubDate: 2015-05-15
      DOI: 10.3390/inorganics3020139
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 155-159: Stayin’
           Alive—Organoplatinum Complexes

    • Authors: Axel Klein
      Pages: 155 - 159
      Abstract: Starting very early, with the findings of Zeise, or Pope and Peachey, organoplatinum complexes were studied intensely in the 1970s and 1980s and were found to be quite stable and very versatile. From then on, the number of publications on organoplatinum complexes has more than doubled in each subsequent decade, and organoplatinum complexes have stretched into many fields of application today. This introduction to the Special Issue on “Organoplatinum Complexes” spans from the history of organoplatinum complexes to the seven manuscripts published in the frame of this Special Issue, representing some of these fields.
      PubDate: 2015-05-19
      DOI: 10.3390/inorganics3020155
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 160-177: Polyoxoniobates and Polyoxotantalates
           as Ligands—Revisited

    • Authors: Pavel Abramov, Maxim Sokolov, Cristian Vicent
      Pages: 160 - 177
      Abstract: This short review summarizes our contribution to the coordination chemistry of noble metals (organometallic fragments of Rh, Ir, Ru and hydroxo Pt(IV)) and polyoxocomplexes of niobium and tantalum.
      PubDate: 2015-05-20
      DOI: 10.3390/inorganics3020160
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 178-193: Biomolecules Electrochemical Sensing
           Properties of a PMo11V@N-Doped Few Layer Graphene Nanocomposite

    • Authors: Diana Fernandes, Marta Nunes, Ricardo Carvalho, Revathi Bacsa, Israel-Martyr Mbomekalle, Philippe Serp, Pedro de Oliveira, Cristina Freire
      Pages: 178 - 193
      Abstract: A novel hybrid nanocomposite, PMo11V@N-doped few layer graphene, was prepared by a one-step protocol through direct immobilization of the tetrabutylammonium salt of a vanadium-substituted phosphomolybdate (PMo11V) onto N-doped few layer graphene (N-FLG). The nanocomposite characterization by FTIR and XPS confirmed its successful synthesis. Glassy carbon modified electrodes with PMo11V and PMo11V@N-FLG showed cyclic voltammograms consistent with surface-confined redox processes attributed to Mo-centred reductions (MoVI→MoV) and a vanadium reduction (VV→VIV). Furthermore, PMo11V@N-FLG modified electrodes showed good stability and well-resolved redox peaks with high current intensities. The observed enhancement of PMo11V electrochemical properties is a consequence of a strong electronic communication between the POM and the N-doped few layer graphene. Additionally, the electro-catalytic and sensing properties towards acetaminophen (AC) and theophylline (TP) were evaluated by voltammetric techniques using a glassy carbon electrode modified with PMo11V@N-FLG. Under the conditions used, the square wave voltammetric peak current increased linearly with AC concentration in the presence of TP, but showing two linear ranges: 1.2 × 10−6 to 1.2 × 10−4 and 1.2 × 10−4 to 4.8 × 10−4 mol dm−3, with different AC sensitivity values, 0.022 A/mol dm−3 and 0.035 A/mol dm−3, respectively (detection limit, DL = 7.5 × 10−7 mol dm−3).
      PubDate: 2015-05-20
      DOI: 10.3390/inorganics3020178
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 194-218: Single-Crystal to Single-Crystal
           Reversible Transformations Induced by Thermal Dehydration in Keggin-Type
           Polyoxometalates Decorated with Copper(II)-Picolinate Complexes: The
           Structure Directing Role of Guanidinium

    • Pages: 194 - 218
      Abstract: Three new hybrid inorganic-metalorganic compounds containing Keggin-type polyoxometalates, neutral copper(II)-picolinate complexes and guanidinium cations have been synthesized in bench conditions and characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction: the isostructural [C(NH2)3]4[{XW12O40}{Cu2(pic)4}]·[Cu2(pic)4(H2O)]2·6H2O [X = Si (1), Ge (3)] and [C(NH2)3]8[{SiW12O40}2{Cu(pic)2}3{Cu2(pic)4(H2O)}2]·8H2O (2). The three compounds show a pronounced two-dimensional character owing to the structure-directing role of guanidinium. In 1 and 3, layers of [{XW12O40}{Cu2(pic)4}]n4n− hybrid POM chains and layers of [Cu2(pic)4(H2O)] complexes and [C(NH2)3]+ cations pack alternately along the z axis. The hydrogen-bonding network established by guanidinium leads to a trihexagonal tiling arrangement of all copper(II)-picolinate species. In contrast, layers of [C(NH2)3]+-linked [{SiW12O40}2{Cu(pic)2}3]n8n− double chains where each Keggin cluster displays a {Cu2(pic)4(H2O)} moiety pointing at the intralamellar space are observed in 2. The thermal stability of 1–3 has been studied by thermogravimetric analyses and variable temperature powder X-ray diffraction. Compounds 1 and 3 undergo single-crystal to single-crystal transformations promoted by reversible dehydration processes and the structures of the corresponding anhydrous phases 1a and 3a have been established. Despite the fact that the [Cu2(pic)4(H2O)] dimeric complexes split into [Cu(pic)2] monomers upon dehydration, the packing remains almost unaltered thanks to the preservation of the hydrogen-bonding network established by guanidinium and its associated Kagome-type lattice. Splitting of the dimeric complexes has been correlated with the electron paramagnetic resonance spectra.
      PubDate: 2015-05-27
      DOI: 10.3390/inorganics3020194
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 219-229: Manganese-Substituted Myoglobin:
           Characterization and Reactivity of an Oxidizing Intermediate towards a
           Weak C-H Bond

    • Authors: Kari Stone, Joey Hua, Humdoon Choudhry
      Pages: 219 - 229
      Abstract: Metal-substituted hemoproteins have been examined by biochemists for decades, but their potential for diverse functionalities has not been thoroughly investigated. By replacing hemoproteins with non-native metals, heme-containing proteins could be capable of performing a range of chemistries not allowed for in the native protein. The metal within the heme of the oxygen-carrying hemoprotein, myoglobin, can readily be replaced with other first row transition metals such as cobalt, chromium and manganese. Upon oxidation with two-electron oxidants (ex. meta-chloroperbenzoic acid), an oxidizing intermediate is produced in manganese-substituted myoglobin. Electron paramagnetic resonance analyses confirm the oxidation of Mn(III) to Mn(IV). With the addition of weak C-H bonds of 1,4 cyclohexadiene, hydrogen atom abstraction is exhibited by the oxidizing intermediate that displays a second-order rate constant of 2.79 +/− 0.22 M−1 s−1 by the metal-oxo species. The replacement of the iron ion with a manganese ion at the active site of myoglobin displays oxidative capabilities that are not shown in native myoglobin.
      PubDate: 2015-05-27
      DOI: 10.3390/inorganics3020219
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 230-245: Understanding the Regioselective
           Hydrolysis of Human Serum Albumin by Zr(IV)-Substituted Polyoxotungstates
           Using Tryptophan Fluorescence Spectroscopy

    • Authors: Vincent Goovaerts, Karen Stroobants, Gregory Absillis, Tatjana Parac-Vogt
      Pages: 230 - 245
      Abstract: The interaction between human serum albumin (HSA) and a series of Zr(IV)-substituted polyoxometalates (POMs) (Lindqvist type POM ((nBu4N)6[{W5O18Zr (μ-OH)}2]·2H2O, Zr2-L2), two Keggin type POMs ((Et2NH2)10[Zr(PW11O39)2]·7H2O, Zr1-K2 and (Et2NH2)8[{α-PW11O39Zr(μ-OH)(H2O)}2]·7H2O, Zr2-K2), and two Wells-Dawson type POMs (K15H[Zr(α2-P2W17O61)2]·25H2O, Zr1-WD2 and Na14[Zr4(P2W16O59)2(μ3-O)2(OH)2(H2O)4]·10H2O, Zr4-WD2) was investigated by tryptophan (Trp) fluorescence spectroscopy. The fluorescence data were analyzed using the Tachiya model, ideally suited for multiple binding site analysis. The obtained quenching constants have the same order of magnitude for all the measured POM:protein complexes, ranging from 1.9 × 105 M−1 to 5.1 × 105 M−1. The number of bound POM molecules to HSA was in the range of 1.5 up to 3.5. The influence of the ionic strength was studied for the Zr1-WD2:HSA complex in the presence of NaClO4. The calculated quenching constant decreases upon increasing the ionic strength of the solution from 0.0004 M to 0.5004 M, indicating the electrostatic nature of the interaction. The number of POM molecules bound to HSA increases from 1.0 to 4.8. 31P NMR spectroscopy provided evidence for the stability of all investigated POM structures during the interaction with HSA.
      PubDate: 2015-05-29
      DOI: 10.3390/inorganics3020230
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 246-266: Synthesis, Characterization and Study
           of Liquid Crystals Based on the Ionic Association of the Keplerate Anion
           [Mo132O372(CH3COO)30(H2O)72]42− and Imidazolium Cations

    • Pages: 246 - 266
      Abstract: A series of eight new materials based on the ionic association between 1-methyl-3-alkylimidazolium cations and the nanometric anionic Keplerate [Mo132O372(CH3COO)30(H2O)72]42− has been prepared and characterized in the solid state. The liquid crystal properties of these materials were investigated by the combination of Polarized Optical Microscopy, Differential Scanning Calorimetry and Small-angle X-Ray Diffraction showing a self-organization in lamellar (L) mesophases for the major part of them. From the interlamellar spacing h and the intercluster distance ahex, we demonstrated that the cations are not randomly organized around the anionic cluster and that the alkyl chains of the cations are certainly folded, which limits the van der Waals interactions between the cations within the liquid crystal phase and therefore harms the quality of the mesophases.
      PubDate: 2015-06-05
      DOI: 10.3390/inorganics3020246
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 267-278: Synthesis and Characterization of
           8-Yttrium(III)-Containing 81-Tungsto-8-Arsenate(III),

    • Authors: Masooma Ibrahim, Bassem Bassil, Ulrich Kortz
      Pages: 267 - 278
      Abstract: The 8-yttrium(III)-containing 81-tungsto-8-arsenate(III) [Y8(CH3COO)(H2O)18(As2W19O68)4(W2O6)2(WO4)]43− (1) has been synthesized in a one-pot reaction of yttrium(III) ions with [B-α-AsW9O33]9− in 1 M NaOAc/HOAc buffer at pH 4.8. Polyanion 1 is composed of four {As2W19O68} units, two {W2O10} fragments, one {WO6} group, and eight YIII ions. The hydrated cesium-sodium salt of 1 (CsNa-1) was characterized in the solid-state by single-crystal XRD, FT-IR spectroscopy, thermogravimetric and elemental analyses.
      PubDate: 2015-06-11
      DOI: 10.3390/inorganics3020267
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 279-294: Fully Oxidized and Mixed-Valent
           Polyoxomolybdates Structured by Bisphosphonates with Pendant Pyridine
           Groups: Synthesis, Structure and Photochromic Properties

    • Pages: 279 - 294
      Abstract: Hybrid organic-inorganic polyoxometalates (POMs) were synthesized in water by the reaction of a MoVI precursor with bisphosphonate ligands functionalized by pyridine groups. The fully oxidized POM [(MoVI3O8)2(O)(O3PC(O)(C3H6NH2CH2C5H4NH)PO3)2]4− has been isolated as water insoluble pure Na salt (NaMo6(Ale-4Py)2) or mixed Na/K salt (NaKMo6(Ale-4Py)2) and their structure solved using single-crystal X-ray diffraction. The mixed-valent complex [(MoV2O4)(MoVI2O6)2{O3PC(O)(C3H6N(CH2C5H4N)2(MoVIO3))PO3}2]8− was obtained as an ammonium salt (NH4Mo6(AlePy2Mo)2), in the presence of a reducing agent (hydrazine). 31P NMR spectroscopic studies in aqueous media have allowed determining the pH stability domain of NH4Mo6(AlePy2Mo)2. NaMo6(Ale-4Py)2 and NaKMo6(Ale-4Py)2 exhibit remarkable solid-state photochromic properties in ambient conditions. Under UV excitation, they develop a very fast color-change from white to deep purple and proved to be the fastest photochromic organoammonium/POM systems. The coloration kinetics has been fully quantified for both salts and is discussed in light of the hydrogen-bonding networks.
      PubDate: 2015-06-11
      DOI: 10.3390/inorganics3020279
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 295-308: Structure Transformation among Deca-,
           Dodeca- and Tridecavanadates and Their Properties for Thioanisole

    • Authors: Yuji Kikukawa, Kazuhiro Ogihara, Yoshihito Hayashi
      Pages: 295 - 308
      Abstract: The transformation of three types of polyoxovanadates, {(n-C4H9)4N}3[H3V10O28], {(n-C4H9)4N}4[V12O32] and {(n-C4H9)4N}3[V13O34] have been investigated according to the rational chemical equations, and the best transformation conditions were reported. By the reaction of [H3V10O28]3− with 0.33 equivalents of {(n-C4H9)4N}OH in acetonitrile at 80 °C, [V12O32]4− was formed with 92% yield. The reaction in nitroethane with 0.69 equivalents of p-toluenesulfonic acid gave [V13O34]3− with 91% yield. The 51V NMR observation of each reaction suggests the complete transformations of [H3V10O28]3− to [V12O32]4− and to [V13O34]3− proceeded without the formation of any byproducts and it provides the reliable synthetic route. Decavanadates were produced by the hydrolysis of [V12O32]4− or [V13O34]3−. While the direct transformation of [V13O34]3− to [V12O32]4− partly proceeded, the reverse one could not be observed. For the thioanisole oxidation, [V13O34]3− showed the highest activity of the three.
      PubDate: 2015-06-17
      DOI: 10.3390/inorganics3020295
      Issue No: Vol. 3, No. 2 (2015)
  • Inorganics, Vol. 3, Pages 19-20: Acknowledgement to Reviewers of
           Inorganics in 2014

    • Authors: Inorganics Office
      Pages: 19 - 20
      Abstract: The editors of Inorganics would like to express their sincere gratitude to the following reviewers for assessing manuscripts in 2014:[...]
      PubDate: 2015-01-08
      DOI: 10.3390/inorganics3010019
      Issue No: Vol. 3, No. 1 (2015)
  • Inorganics, Vol. 3, Pages 21-26: A New Nanometer-Sized
           Ga(III)-Oxyhydroxide Cation

    • Authors: William Casey, Marilyn Olmstead, Caitlyn Hazlett, Chelsey Lamar, Tori Forbes
      Pages: 21 - 26
      Abstract: A new 30-center Ga(III)-oxy-hydroxide cation cluster was synthesized by hydrolysis of an aqueous GaCl3 solution near pH = 2.5 and crystallized using 2,6-napthalene disulfonate (NDS). The cluster has 30 metal centers and a nominal stoichiometry: [Ga30(μ4-O)12(μ3-O)4(μ3-OH)4(μ2-OH)42(H2O)16](2,6-NDS)6, where 2,6-NDS = 2,6-napthalene disulfonate This cluster augments the very small library of Group 13 clusters that have been isolated from aqueous solution and closely resembles one other Ga(III) cluster with 32 metal centers that had been isolated using curcurbit ligands. These clusters have uncommon linked Ga(O)4 centers and sets of both protonated and unprotonated μ3-oxo.
      PubDate: 2015-02-03
      DOI: 10.3390/inorganics3010021
      Issue No: Vol. 3, No. 1 (2015)
  • Inorganics, Vol. 3, Pages 27-39: [AuHg(o-C6H4PPh2)2I]: A Dinuclear
           Heterometallic Blue Emitter

    • Pages: 27 - 39
      Abstract: The heteronuclear AuI/HgII complex [AuHg(o-C6H4PPh2)2I] (1) was prepared by reacting of [Hg(2-C6H4PPh2)2] with [Au(tht)2]ClO4 (1:1) and NaI in excess. The heterometallic compound 1 has been structurally characterized and shows an unusual blue luminescent emission in the solid state. Theoretical calculations suggest that that the origin of the emission arises from the iodide ligand arriving at metal-based orbitals in a Ligand to Metal-Metal Charge Transfer transition.
      PubDate: 2015-02-11
      DOI: 10.3390/inorganics3010027
      Issue No: Vol. 3, No. 1 (2015)
  • Inorganics, Vol. 3, Pages 40-54: Disulfide Competition for Phosphine
           Gold(I) Thiolates: Phosphine Oxide Formation vs. Thiolate Disulfide

    • Authors: Gamage Garusinghe, S. Bessey, Mostapha Aghamoosa, Meaghan McKinnon, Alice Bruce, Mitchell Bruce
      Pages: 40 - 54
      Abstract: Phosphine gold(I) thiolate complexes react with aromatic disulfides via two pathways: either thiolate–disulfide exchange or a pathway that leads to formation of phosphine oxide. We have been investigating the mechanism of gold(I) thiolate–disulfide exchange. Since the formation of phosphine oxide is a competing reaction, it is important for our kinetic analysis to understand the conditions under which phosphine oxide forms. 1H and 31P{1H} NMR, and GC-MS techniques were employed to study the mechanism of formation of phosphine oxide in reactions of R3PAu(SRʹ) (R = Ph, Et; SRʹ = SC6H4CH3, SC6H4Cl, SC6H4NO2, or tetraacetylthioglucose (TATG)) and R*SSR* (SR* = SC6H4CH3, SC6H4Cl, SC6H4NO2, or 2-nitrobenzoic acid). The phosphine oxide pathway is most significant for disulfides with strongly electron withdrawing groups and in high dielectric solvents, such as DMSO. Data suggest that phosphine does not dissociate from gold(I) prior to reaction with disulfide. 2D (1H-1H) NMR ROESY experiments are consistent with an intermediate in which the disulfide and phosphine gold(I) thiolate are in close proximity. Water is necessary but not sufficient for formation of phosphine oxide since no phosphine oxide forms in acetonitrile, a solvent, which frequently contains water.
      PubDate: 2015-02-27
      DOI: 10.3390/inorganics3010040
      Issue No: Vol. 3, No. 1 (2015)
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