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Journal Cover Inorganics
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   ISSN (Online) 2304-6740
   Published by MDPI Homepage  [148 journals]
  • Inorganics, Vol. 5, Pages 18: Adsorption and Oxidation of Aromatic Amines
           on Metal(II) Hexacyanocobaltate(III) Complexes: Implication for
           Oligomerization of Exotic Aromatic Compounds

    • Authors: Rachana Sharma, Md. Asif Iqubal, Sohan Jheeta, Kamaluddin
      First page: 18
      Abstract: Based on the hypothesis on the presence of double metal cyanides in the primordial oceans, a series of nano-sized metal(II) hexacyanocobaltate(III) (MHCCo) with the general formula: M3[Co(CN)6]2•xH2O (where M = Zn, Fe, Ni and Mn) has been synthesized. Surface interaction of aromatic amines, namely aniline, 4-chloroaniline, 4-methylaniline and 4-methoxyaniline with MHCCo particles has been carried out at the concentration range of 100–400 μM at pH~7.0. The percentage binding of aromatic amines on MHCCo surface was found to be in the range of 84%–44%. The trend in adsorption was in accordance to the relative basicity of the studied amines. At the experimental pH, amines reacted rapidly with the surface of the iron(II) hexacyanocobaltate, producing colored products that were analyzed by Gas Chromatography Mass Spectroscopy (GC-MS). GC-MS analysis of the colored products demonstrated the formation of dimers of the studied aromatic amines. Surface interaction of aromatic amines with MHCCo was studied by Fourier Transform Infrared (FT-IR) spectroscopy and Field Emission Scanning Electron Microscopy (FE-SEM). The change in amine characteristic frequencies, as observed by FT-IR, suggests that interaction took place through the NH2 group on amines with metal ions of hexacyanocobaltate complexes. FE-SEM studies revealed the adherence of 4-methoxyaniline on zinc hexacyanocobaltate particles surface. We proposed that MHCCo might have been formed under the conditions on primitive Earth and may be regarded as an important candidate for concentrating organic molecules through the adsorption process.
      PubDate: 2017-03-24
      DOI: 10.3390/inorganics5020018
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 19: Na1+yVPO4F1+y (0 ≤ y≤ 0.5) as Cathode
           Materials for Hybrid Na/Li Batteries

    • Authors: Nina Kosova, Daria Rezepova
      First page: 19
      Abstract: Using Rietveld-refined X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and electrochemical cycling, it was established that among sodium vanadium fluorophosphate compositions Na1+yVPO4F1+y (0 ≤ y ≤ 0.75), the single-phase material Na1.5VPO4F1.5 or Na3V2(PO4)2F3 with a tetragonal structure (the P42/mnm S.G.) is formed only for y = 0.5. The samples with y < 0.5 and y > 0.5 possessed different impurity phases. Na3V2(PO4)2F3 could be considered as a multifunctional cathode material for the fabrication of lithium-ion and sodium-ion high-energy batteries. The reversible discharge capacity of 116 mAh•g−1 was achieved upon cycling Na3V2(PO4)2F3 in a hybrid Na/Li cell. Decrease in discharge capacity for the other samples was in accordance with the amount of the electrochemically active phase Na3V2(PO4)2F3. Na3V2(PO4)2F3 showed good cycleability and a high rate of performance, presumably due to operation in the mixed Na/Li electrolyte. The study of the structure and composition of charged and discharged samples, and the analysis of differential capacity curves showed a negligible Na/Li electrochemical exchange, and a predominant sodium-based cathode reaction. To increase the degree of the Na/Li electrochemical exchange in Na3V2(PO4)2F3, it needs to be desodiated first in a Na cell, and then cycled in a lithium cell. In this case, the electrolyte would be enriched with the Li ions.
      PubDate: 2017-03-27
      DOI: 10.3390/inorganics5020019
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 20: Investigation of the Structures and Energy
           Landscapes of Thiocyanate-Water Clusters

    • Authors: Lewis Smeeton, John Hey, Roy Johnston
      First page: 20
      Abstract: The Basin Hopping search method is used to find the global minima (GM) and map the energy landscapes of thiocyanate-water clusters, (SCN−)(H2O)n with 3–50 water molecules, with empirical potentials describing the ion-water and water-water interactions. (It should be noted that beyond n = 23, the lowest energy structures were only found in 1 out of 8 searches so they are unlikely to be the true GM but are indicative low energy structures.) As for pure water clusters, the low energy isomers of thiocyanate-water clusters show a preponderance of fused water cubes and pentagonal prisms, with the weakly solvated thiocyanate ion lying on the surface, replacing two water molecules along an edge of a water polyhedron and with the sulfur atom in lower coordinated sites than nitrogen. However, by comparison with Density Functional Theory (DFT) calculations, the empirical potential is found to overestimate the strength of the thiocyanate-water interaction, especially O–H⋯S, with low energy DFT structures having lower coordinate N and (especially) S atoms than for the empirical potential. In the case of these finite ion-water clusters, the chaotropic (“disorder-making”) thiocyanate ion weakens the water cluster structure but the water molecule arrangement is not significantly changed.
      PubDate: 2017-03-31
      DOI: 10.3390/inorganics5020020
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 21: Photophysics of BODIPY Dyes as
           Readily-Designable Photosensitisers in Light-Driven Proton Reduction

    • Authors: Laura Dura, Maria Wächtler, Stephan Kupfer, Joachim Kübel, Johannes Ahrens, Sebastian Höfler, Martin Bröring, Benjamin Dietzek, Torsten Beweries
      First page: 21
      Abstract: A series of boron dipyrromethene (BODIPY) dyes was tested as photosensitisers for light-driven hydrogen evolution in combination with the complex [Pd(PPh3)Cl2]2 as a source for catalytically-active Pd nanoparticles and triethylamine as a sacrificial electron donor. In line with earlier reports, halogenated dyes showed significantly higher hydrogen production activity. All BODIPYs were fully characterised using stationary absorption and emission spectroscopy. Time-resolved spectroscopic investigations on meso-mesityl substituted compounds revealed that reduction of the photo-excited BODIPY by the sacrificial agent occurs from an excited singlet state, while, in halogenated species, long-lived triplet states are present, determining electron transfer processes from the sacrificial agent. Quantum chemical calculations performed at the time-dependent density functional level of theory indicate that the differences in the photocatalytic performance of the present series of dyes can be correlated to the varying efficiency of intersystem crossing in non-halogenated and halogenated species and not to alterations in the energy levels introduced upon substitution.
      PubDate: 2017-04-05
      DOI: 10.3390/inorganics5020021
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 22: Insights into Molecular
           Beryllium–Silicon Bonds

    • Authors: Dominik Naglav, Briac Tobey, Kevin Dzialkowski, Georg Jansen, Christoph Wölper, Stephan Schulz
      First page: 22
      Abstract: We present the synthesis of two silyl beryllium halides HypSiBeX∙(thf) (HypSi = Si(SiMe3)3, X = Cl 2a, I 4a) and the molecular structure of 2a as determined by single crystal X-ray diffraction. Compounds 2a and 4a were characterized via multi-nuclear NMR spectroscopy (1H, 9Be, 13C, 29Si), and the bonding situation was further investigated using quantum chemical calculations (with the addition of further halides X = F 1b, Cl 2b, Br 3b, I 4b). The nature of the beryllium silicon bond in the context of these compounds is highlighted and discussed.
      PubDate: 2017-04-10
      DOI: 10.3390/inorganics5020022
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 23: Chemical Tuning and Absorption Properties of
           Iridium Photosensitizers for Photocatalytic Applications

    • Authors: Olga Bokareva, Tobias Möhle, Antje Neubauer, Sergey Bokarev, Stefan Lochbrunner, Oliver Kühn
      First page: 23
      Abstract: Cyclometalated Ir(III) complexes are of particular interest due to the wide tunability of their electronic structure via variation of their ligands. Here, a series of heteroleptic Ir-based photosensitizers with the general formula [Ir(C^N)2(N^N)]+ has been studied theoretically by means of an optimally-tuned long-range separated density functional. Focusing on the steady-state absorption spectra, correlations between the chemical modification of both ligand types with the natures of the relevant dark and bright electronic states are revealed. Understanding such correlations builds up a basis for the rational design of efficient photocatalytic systems.
      PubDate: 2017-04-12
      DOI: 10.3390/inorganics5020023
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 24: Visible Light-Activated PhotoCORMs

    • Authors: Emmanuel Kottelat, Zobi Fabio
      First page: 24
      Abstract: Despite its well-known toxicity, carbon monoxide (CO) is now recognized as a potential therapeutic agent. Its inherent toxicity, however, has limited clinical applications because uncontrolled inhalation of the gas leads to severe systemic derangements in higher organisms. In order to obviate life-threatening effects and administer the gas by bypassing the respiratory system, CO releasing molecules (CORMs) have emerged in the last decades as a plausible alternative to deliver controlled quantities of CO in cellular systems and tissues. As stable, solid-storage forms of CO, CORMs can be used to deliver the gas following activation by a stimulus. Light-activated CORMs, known as photoCORMs, are one such example. This class of molecules is particularly attractive because, for possible applications of CORMs, temporal and spatial control of CO delivery is highly desirable. However, systems triggered by visible light are rare. Most currently known photoCORMs are activated with UV light, but red light or even infrared photo-activation is required to ensure that structures deeper inside the body can be reached while minimizing photo-damage to healthy tissue. Thus, one of the most challenging chemical goals in the preparation of new photoCORMs is the reduction of radiation energy required for their activation, together with strategies to modulate the solubility, stability and nontoxicity of the organic or organometallic scaffolds. In this contribution, we review the latest advances in visible light-activated photoCORMs, and the first promising studies on near-infrared light activation of the same.
      PubDate: 2017-04-13
      DOI: 10.3390/inorganics5020024
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 25: Nanotechnology of Positive Electrodes for
           Li-Ion Batteries

    • Authors: Xiaoyu Zhang, Ana-Gabriela Porras-Gutierrez, Alain Mauger, Henri Groult, Christian Julien
      First page: 25
      Abstract: This work presents the recent progress in nanostructured materials used as positive electrodes in Li-ion batteries (LIBs). Three classes of host lattices for lithium insertion are considered: transition-metal oxides V2O5, α-NaV2O5, α-MnO2, olivine-like LiFePO4, and layered compounds LiNi0.55Co0.45O2, LiNi1/3Mn1/3Co1/3O2 and Li2MnO3. First, a brief description of the preparation methods shows the advantage of a green process, i.e., environmentally friendliness wet chemistry, in which the synthesis route using single and mixed chelators is used. The impact of nanostructure and nano-morphology of cathode material on their electrochemical performance is investigated to determine the synthesis conditions to obtain the best electrochemical performance of LIBs.
      PubDate: 2017-04-14
      DOI: 10.3390/inorganics5020025
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 26: Potassium C–F Interactions and the
           Structural Consequences in N,N′-Bis(2,6-difluorophenyl)formamidinate

    • Authors: Daniel Werner, Glen Deacon, Peter Junk
      First page: 26
      Abstract: Treatment of K[N(SiMe3)2] with N,N′-bis(2,6-difluorophenyl)formamidine (DFFormH) in toluene, resulted in the formation of [K(DFForm)]∞ (1) as a poorly soluble material. Upon dissolution in thf and layering with n-hexane, 1 was crystallised and identified as a two-dimensional polymer, in which all fluorine and nitrogen atoms, and also part of one aryl group, bridge between four symmetry equivalent potassium ions, giving rise to a completely unique μ4-(N,N′,F,F′):(N,N′):η4(Ar-C(2,3,4,5,6)):(F″,F′′′) DFForm coordination. The two-dimensional nature of the polymer could be deconstructed to one dimension by crystallisation from neat thf at −35 °C, giving [K2(DFForm)2(thf)2]∞ (2), where the thf molecules bridge the monomeric units. Complete polymer dissociation was observed when 1 was crystallised from toluene/n-hexane mixtures in the presence of 18-crown-6, giving [K(DFForm)(18-crown-6)] (3), which showed unprecedented κ(N,Cispo,F) DFForm coordination, rather than the expected κ(N,N′) coordination.
      PubDate: 2017-04-17
      DOI: 10.3390/inorganics5020026
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 27: Pulsed Current Electrodeposition of Silicon
           Thin Films Anodes for Lithium Ion Battery Applications

    • Authors: Bharat Gattu, Rigved Epur, Pavithra Shanti, Prashanth Jampani, Ramalinga Kuruba, Moni Datta, Ayyakkannu Manivannan, Prashant Kumta
      First page: 27
      Abstract: Electrodeposition of amorphous silicon thin films on Cu substrate from organic ionic electrolyte using pulsed electrodeposition conditions has been studied. Scanning electron microscopy analysis shows a drastic change in the morphology of these electrodeposited silicon thin films at different frequencies of 0, 500, 1000, and 5000 Hz studied due to the change in nucleation and the growth mechanisms. These electrodeposited films, when tested in a lithium ion battery configuration, showed improvement in stability and performance with an increase in pulse current frequency during deposition. XPS analysis showed variation in the content of Si and oxygen with the change in frequency of deposition and with the change in depth of these thin films. The presence of oxygen largely due to electrolyte decomposition during Si electrodeposition and the structural instability of these films during the first discharge–charge cycle are the primary reasons contributing to the first cycle irreversible (FIR) loss observed in the pulse electrodeposited Si–O–C thin films. Nevertheless, the silicon thin films electrodeposited at a pulse current frequency of 5000 Hz show a stable capacity of ~805 mAh·g−1 with a fade in capacity of ~0.056% capacity loss per cycle (a total loss of capacity ~246 mAh·g−1) at the end of 500 cycles.
      PubDate: 2017-04-20
      DOI: 10.3390/inorganics5020027
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 28: Alkali and Alkaline Earth Metal Complexes
           Ligated by an Ethynyl Substituted Cyclopentadienyl Ligand

    • Authors: Tim Seifert, Peter Roesky
      First page: 28
      Abstract: Sodium, potassium, and calcium compounds of trimethyl((2,3,4,5-tetramethylcyclopentadien-1-yl)ethynyl)silane (CpMe4(C≡CSiMe3)) were synthesized and characterized by X-ray diffraction and standard analytical methods. The sodium derivative was obtained by deprotonation of CpMe4(C≡CSiMe3)H with Na{N(SiMe3)2} to give a monomeric complex [NaCpMe4(C≡CSiMe3)(THF)3]. In a similar reaction, starting from K{N(SiMe3)2} the corresponding potassium compound [KCpMe4(C≡CSiMe3)(THF)2]n, which forms a polymeric super sandwich structure in the solid state, was obtained. Subsequently, salt metathesis reactions were conducted in order to investigate the versatility of the CpMe4(C≡CSiMe3)− ligand in alkaline earth chemistry. The reaction of [KCpMe4(C≡CSiMe3)(THF)2]n with CaI2 afforded the dimeric complex [CaCpMe4(C≡CSiMe3)I(THF)2]2, in which both CpMe4(C≡CSiMe3)Ca units are bridged by iodide in a μ2 fashion. In-depth NMR investigation indicates that [CaCpMe4(C≡CSiMe3)I(THF)2]2 is in a Schlenk equilibrium with [{CpMe4(C≡CSiMe3)}2Ca(THF)x] and CaI2(THF)2, as is already known for [CaCp*I(THF)2].
      PubDate: 2017-04-20
      DOI: 10.3390/inorganics5020028
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 29: Methanediide Formation via Hydrogen
           Elimination in Magnesium versus Aluminium Hydride Complexes of a
           Sterically Demanding Bis(iminophosphoranyl)methanediide

    • Authors: Christian Sindlinger, Samuel Lawrence, David Cordes, Alexandra Slawin, Andreas Stasch
      First page: 29
      Abstract: Substituted bis(iminophosphoranyl)methanes are CH acidic compounds that can form complexes with formally dianionic central carbon centres. The reaction of H2C(Ph2P=NDip)2 (≡ H2L), Dip = 2,6-diisopropylphenyl, with one equivalent of di-n-butylmagnesium afforded the methanide complex [HLMgnBu] 1. Treatment of Complex 1 with phenylsilane in aromatic solvents at elevated temperatures afforded the methanediide complex [(LMg)2] 2 presumably via the MgH intermediate [(HLMgH)n] (n = 1 or 2). The reaction of 1 with LiAlH4 in diethyl ether yielded the AlH complex [HLAlH2] 3. Alternatively, this complex was also obtained from the reaction of H2L with AlH3∙NMe3. The molecular structures of [HLMgnBu] 1, [(LMg)2] 2, and [HLAlH2] 3 are reported. Complex 3 shows no sign of H2 elimination to a methanediide species at elevated temperatures in contrast to the facile elimination of the putative reaction intermediate [(HLMgH)n] (n = 1 or 2) to form [(LMg)2] 2. The chemical properties of Complex 2 were investigated, and this complex appears to be stable against coordination with strong donor molecules.
      PubDate: 2017-04-22
      DOI: 10.3390/inorganics5020029
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 30: Backbone-Substituted β-Ketoimines and
           Ketoiminate Clusters: Transoid Li2O2 Squares and D2-Symmetric Li4O4
           Cubanes. Synthesis, Crystallography and DFT Calculations

    • Authors: Twyla Gietz, René Boeré
      First page: 30
      Abstract: The preparation and crystal structures of four β-ketoimines with bulky aryl nitrogen substituents (2,6-diisopropylphenyl and 2,4,6-trimethylphenyl) and varying degrees of backbone methyl substitution are reported. Backbone substitution “pinches” the chelate ring. Deprotonation with n-butyllithium leads to dimeric Li2O2 clusters, as primary laddered units, with an open transoid geometry as shown by crystal structures of three examples. The coordination sphere of each lithium is completed by one tetrahydrofuran ligand. NMR spectra undertaken in either C6D6 or 1:1 C6D6/d8-THF show free THF in solution and the chemical shifts of ligand methyl groups experience significant ring-shielding which can only occur from aryl rings on adjacent ligands. Both features point to conversion to higher-order aggregates when the THF concentration is reduced. Recrystallization of the materials from hydrocarbon solutions results in secondary laddering as tetrameric Li4O4 clusters with a cuboidal core, three examples of which have been crystallographically characterised. These clusters are relatively insoluble and melt up to 250 °C; a consideration of the solid-state structures indicates that the clusters with 2,6-diisopropylphenyl substituents form very uniform ball-like molecular structures that will only be weakly solvated.
      PubDate: 2017-04-26
      DOI: 10.3390/inorganics5020030
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 31: Hydrogen Sorption in Erbium Borohydride
           Composite Mixtures with LiBH4 and/or LiH

    • Authors: Michael Heere, Seyed GharibDoust, Matteo Brighi, Christoph Frommen, Magnus Sørby, Radovan Černý, Torben Jensen, Bjørn Hauback
      First page: 31
      Abstract: Rare earth (RE) metal borohydrides have recently been receiving attention as possible hydrogen storage materials and solid-state Li-ion conductors. In this paper, the decomposition and reabsorption of Er(BH4)3 in composite mixtures with LiBH4 and/or LiH were investigated. The composite of 3LiBH4 + Er(BH4)3 + 3LiH has a theoretical hydrogen storage capacity of 9 wt %, nevertheless, only 6 wt % hydrogen are accessible due to the formation of thermally stable LiH. Hydrogen sorption measurements in a Sieverts-type apparatus revealed that during three desorption-absorption cycles of 3LiBH4 + Er(BH4)3 + 3LiH, the composite desorbed 4.2, 3.7 and 3.5 wt % H for the first, second and third cycle, respectively, and thus showed good rehydrogenation behavior. In situ synchrotron radiation powder X-ray diffraction (SR-PXD) after ball milling of Er(BH4)3 + 6LiH resulted in the formation of LiBH4, revealing that metathesis reactions occurred during milling in these systems. Impedance spectroscopy of absorbed Er(BH4)3 + 6LiH showed an exceptional high hysteresis of 40–60 K for the transition between the high and low temperature phases of LiBH4, indicating that the high temperature phase of LiBH4 is stabilized in the composite.
      PubDate: 2017-04-26
      DOI: 10.3390/inorganics5020031
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 32: Study of Cathode Materials for Lithium-Ion
           Batteries: Recent Progress and New Challenges

    • Authors: Florian Schipper, Prasant Nayak, Evan Erickson, S. Amalraj, Onit Srur-Lavi, Tirupathi Penki, Michael Talianker, Judith Grinblat, Hadar Sclar, Ortal Breuer, Christian Julien, Nookala Munichandraiah, Daniela Kovacheva, Mudit Dixit, Dan Major, Boris Markovsky, Doron Aurbach
      First page: 32
      Abstract: Amongst a number of different cathode materials, the layered nickel-rich LiNiyCoxMn1−y−xO2 and the integrated lithium-rich xLi2MnO3·(1 − x)Li[NiaCobMnc]O2 (a + b + c = 1) have received considerable attention over the last decade due to their high capacities of ~195 and ~250 mAh·g−1, respectively. Both materials are believed to play a vital role in the development of future electric vehicles, which makes them highly attractive for researchers from academia and industry alike. The review at hand deals with both cathode materials and highlights recent achievements to enhance capacity stability, voltage stability, and rate capability, etc. The focus of this paper is on novel strategies and established methods such as coatings and dopings.
      PubDate: 2017-04-28
      DOI: 10.3390/inorganics5020032
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 33: Hetero- and Homoleptic Magnesium Triazenides

    • Authors: Denis Vinduš, Mark Niemeyer
      First page: 33
      Abstract: Using monoanionic triazenide ligands derived from biphenyl and m-terphenyl substituted triazenes Dmp(Tph)N3H (1a), (Me4Ter)2N3H (1b) or Dmp(Mph)N3H (1c) (Dmp = 2,6-Mes2C6H3 with Mes = 2,4,6-Me3C6H2; Me4Ter = 2,6-(3,5-Me2C6H3)2C6H3; Mph = 2-MesC6H4; Tph = 2-TripC6H4 with Trip = 2,4,6-i-Pr3C6H2), several magnesium triazenides were synthesized. Heteroleptic complexes [Mg(N3Ar2)I(OEt2)] (Ar2 = Dmp/Tph (2a), (Me4Ter)2 (2b) were obtained from metalation of the corresponding triazenes with di-n-butylmagnesium followed by reaction with iodine in diethyl ether as the solvent in high yields. Replacing diethyl ether by n-heptane afforded trinuclear compounds [Mg3(N3Ar2)2I4] (3a, 3b) in low yields in which a central MgI2 fragment is coordinated by two iodomagnesium triazenide moieties. Two unsolvated homoleptic magnesium compounds [Mg(N3Ar2)2] (4b, 4c) were obtained from di-n-butylmagnesium and triazenes 1b or 1c in a 1:2 ratio. Depending on the nature of the substituents, the magnesium center either shows the expected tetrahedral or a rather unusual square planar coordination.
      PubDate: 2017-05-01
      DOI: 10.3390/inorganics5020033
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, Pages 34: Dye-Sensitized Photocatalytic Water
           Splitting and Sacrificial Hydrogen Generation: Current Status and Future

    • Authors: Pankaj Chowdhury, Ghodsieh Malekshoar, Ajay Ray
      First page: 34
      Abstract: Today, global warming and green energy are important topics of discussion for every intellectual gathering all over the world. The only sustainable solution to these problems is the use of solar energy and storing it as hydrogen fuel. Photocatalytic and photo-electrochemical water splitting and sacrificial hydrogen generation show a promise for future energy generation from renewable water and sunlight. This article mainly reviews the current research progress on photocatalytic and photo-electrochemical systems focusing on dye-sensitized overall water splitting and sacrificial hydrogen generation. An overview of significant parameters including dyes, sacrificial agents, modified photocatalysts and co-catalysts are provided. Also, the significance of statistical analysis as an effective tool for a systematic investigation of the effects of different factors and their interactions are explained. Finally, different photocatalytic reactor configurations that are currently in use for water splitting application in laboratory and large scale are discussed.
      PubDate: 2017-05-18
      DOI: 10.3390/inorganics5020034
      Issue No: Vol. 5, No. 2 (2017)
  • Inorganics, Vol. 5, 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 2016.[...]
      PubDate: 2017-01-10
      DOI: 10.3390/inorganics5010003
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 4: Anticancer Applications and Recent
           Investigations of Metallodrugs Based on Gallium, Tin and Titanium

    • Authors: Younes Ellahioui, Sanjiv Prashar, Santiago Gómez-Ruiz
      First page: 4
      Abstract: For more than 100 years metal complexes have been extensively used in therapy and since the discovery of cisplatin the research in this field has expanded exponentially. The scientific community is always in search of new alternatives to platinum compounds and a wide variety of metallodrugs based on other metals have been reported with excellent therapeutic results. This short review focuses on the work that our research group has carried out since 2007 in collaboration with others and centers on the preparation of organogallium(III) compounds, organotin(IV) derivatives, and titanocene(IV) complexes together with the study of their cytotoxic anticancer properties.
      PubDate: 2017-01-12
      DOI: 10.3390/inorganics5010004
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 5: P-Fluorous Phosphines as
           Electron-Poor/Fluorous Hybrid Functional Ligands for Precious Metal
           Catalysts: Synthesis of Rh(I), Ir(I), Pt(II), and Au(I) Complexes Bearing
           P-Fluorous Phosphine Ligands

    • Authors: Shin-ichi Kawaguchi, Yuta Saga, Yuki Sato, Yoshiaki Minamida, Akihiro Nomoto, Akiya Ogawa
      First page: 5
      Abstract: P-Fluorous phosphine (R2PRf), in which the perfluoroalkyl group is directly bonded to the phosphorus atom, is a promising ligand because it has a hybrid functionality, i.e., electron-poor and fluorous ligands. However, examples of P-fluorous phosphine–metal complexes are still rare, most probably because the P-fluorous group is believed to decrease the coordination ability of the phosphines dramatically. In contrast, however, we have succeeded in synthesizing a series of P-fluorous phosphine–coordinated metal complexes such as rhodium, iridium, platinum, and gold. Furthermore, the electronic properties of R2PnC10F21 are investigated by X-ray analysis of PtCl2(Ph2PnC10F21)2 and the infrared CO stretching frequency of RhCl(CO)(R2PnC10F21)2. IrCl(CO)(Ph2PnC10F21)2- and AuCl(R2PnC10F21)-catalyzed reactions are also demonstrated.
      PubDate: 2017-01-12
      DOI: 10.3390/inorganics5010005
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 6: Influence of Fatty Acid Alkyl Chain Length on
           Anisotropy of Copper Nitride Nano-Crystallites

    • Authors: Takashi Nakamura
      First page: 6
      Abstract: My group developed a simple method to prepare copper nitride fine particles from copper carboxylate in a solvent of long-chain alcohols without the use of high temperatures or high pressures. By selecting copper acetate or copper decanoate as the copper source, my group demonstrated that the morphology of the copper nitride fine particles varied between cubic and plate-like, respectively. Although a hypothesis was proposed to explain the influence of the length of the alkyl chain on the copper decanoate, it is uncertain how much the chain length influences the shape of the fine particles. In this work, I demonstrated the effect of the length of the alkyl chain on particle shape by preparing fine particles from a series of copper sources with different alky chain lengths and characterizing the particles with x-ray diffractometry (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The main findings were as follows: (1) the fine particles were plate-like when the alkyl chain length exceeded 5; (2) the aspect ratio of the plate-like particles increased as the alkyl chain length increased; and (3) growth of the (110) and (111) planes of the copper nitride crystal were selectively inhibited.
      PubDate: 2017-01-16
      DOI: 10.3390/inorganics5010006
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 7: Hydrothermal Treatment of Tannin: A Route to
           Porous Metal Oxides and Metal/Carbon Hybrid Materials

    • Authors: Flavia Braghiroli, Vanessa Fierro, Andrzej Szczurek, Philippe Gadonneix, Jaafar Ghanbaja, Julien Parmentier, Ghouti Medjahdi, Alain Celzard
      First page: 7
      Abstract: In the present paper, porous materials were prepared from the hydrothermal treatment of aqueous solutions of tannin, a renewable phenolic resource extracted from tree barks, containing dissolved salts of transition metals: V, Cr, Ni and Fe. Hydrothermal treatment produced carbonaceous particles doped with the aforementioned metals, and such materials were treated according to two different routes: (i) calcination in air in order to burn the carbon and to recover porous oxides; (ii) pyrolysis in inert atmosphere so as to recover porous metal/carbon hybrid materials. The nature of the metal salt was found to have a dramatic impact on the structure of the materials recovered by the first route, leading either to nano-powders (V, Cr) or to hollow microspheres (Ni, Fe). The second route was only investigated with iron, leading to magnetic Fe-loaded micro/mesoporous carbons whose texture, pore volumes and surface areas gradually changed with the iron content.
      PubDate: 2017-01-24
      DOI: 10.3390/inorganics5010007
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 8: Manganese(I)-Based CORMs with 5-Substituted
           3-(2-Pyridyl)Pyrazole Ligands

    • Authors: Ralf Mede, Steve Gläser, Benedikt Suchland, Björn Schowtka, Miles Mandel, Helmar Görls, Sven Krieck, Alexander Schiller, Matthias Westerhausen
      First page: 8
      Abstract: The reaction of [(OC)5MnBr] with substituted 3-(2-pyridyl)pyrazoles) 2-PyPzRH (1a-l) in methanol or diethyl ether yields the yellow to orange manganese(I) complexes [(OC)3Mn(Br)(2-PyPzRH)] (2a-l), the substituents R being phenyl (a), 1-naphthyl (b), 2-anthracenyl (c), 1-pyrenyl (d), 4-bromophenyl (e), 3-bromophenyl (f), duryl (g), 2-pyridyl (h), 2-furanyl (i), 2-thienyl (j), ferrocenyl (k), and 1-adamantyl (l). The carbonyl ligands are arranged facially, leading to three chemically different CO ligands due to different trans-positioned Lewis donors. The diversity of the substituent R demonstrates that this photoCORM backbone can easily be varied with a negligible influence on the central (OC)3MnBr fragment, because the structural parameters and the spectroscopic data of this unit are very similar for all these derivatives. Even the ferrocenyl complex 2k shows a redox potential for the ferrocenyl subunit which is identical to the value of the free 5-ferrocenyl-3-(2-pyridyl)pyrazole (1k). The ease of variation of the starting 5-substituted 3-(2-pyridyl)pyrazoles) offers a modular system to attach diverse substituents at the periphery of the photoCORM complex.
      PubDate: 2017-01-25
      DOI: 10.3390/inorganics5010008
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 9: Flux Synthesis, Crystal Structures, and
           Magnetism of the Series La2n+2MnSen+2O2n+2 (n = 0–2)

    • Authors: Simon Peschke, Dirk Johrendt
      First page: 9
      Abstract: Three members of the homologous series of manganese oxyselenides with the general formula La2n+2MnSen+2O2n+2 (n = 0–2) have been synthesized in a NaI/KI flux and characterized by single-crystalX-raydiffraction,powderX-raydiffractionandmagneticmeasurements. Thestructures consist of chains of edge-sharing MnSe4O2-octahedra along the b-axis which are linked together along the a-axis by edge-sharing OLa4- and/or OLa3Mn-tetrahedra forming infinite ribbons of increasing width. mC-La2MnSe2O2 (Pb2HgCl2O2-type, C2/m, a = 11.6621(5) Å, b = 3.9719(1) Å, c = 7.2049(3) Å, β = 121.655(2)◦) represents a new polymorph of this compound. La4MnSe3O4 (P2/m, a = 9.0055(4) Å, b = 4.0186(1) Å, c = 7.1946(3) Å, β = 109.715(2)◦) and La6MnSe4O6 (C2/m, a = 24.760(2) Å,b = 4.0359(3)Å,c=7.1850(6)Å, β =104.162(3)◦)exhibitnewstructuretypes. Magnetic measurements suggest antiferromagnetic order of the moments below about 15 K with effective magnetic moments of 5.53(1), 5.99(1) and 6.01(1) µB per formula unit for n = 1, 2 and 3, respectively.
      PubDate: 2017-01-31
      DOI: 10.3390/inorganics5010009
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 10: Synthesis, Crystal Structure, Polymorphism,
           and Magnetism of Eu(CN3H4)2 and First Evidence of EuC(NH)3

    • Authors: Arno Görne, Janine George, Jan van Leusen, Richard Dronskowski
      First page: 10
      Abstract: We report the first magnetically coupled guanidinate, α-Eu(CN3H4)2 (monoclinic, P21, a = 5.8494(3) Å, b = 14.0007(8) Å, c = 8.4887(4) Å, β = 91.075(6)°, V = 695.07(6) Å3, Z = 4). Its synthesis, polymorphism, crystal structure, and properties are complemented and supported by density-functional theory (DFT) calculations. The α-, β- and γ-polymorphs of Eu(CN3H4)2 differ in powder XRD, while the γ-phase transforms into the β-form over time. In α-Eu(CN3H4)2, Eu is octahedrally coordinated and sits in one-dimensional chains; the guanidinate anions show a hydrogen-bonding network. The different guanidinate anions are theoretically predicted to adopt syn-, anti- and all-trans-conformations. Magnetic measurements evidence ferromagnetic interactions, presumably along the Eu chains. Finally, EuC(NH)3 (isostructural to SrC(NH)3 and YbC(NH)3, hexagonal, P63/m, a = 5.1634(7) Å, c = 7.1993(9) Å, V = 166.23(4) Å3, Z = 2) is introduced as a possible ferromagnet.
      PubDate: 2017-02-07
      DOI: 10.3390/inorganics5010010
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 11: Structural Study of Mismatched Disila-Crown
           Ether Complexes

    • Authors: Kirsten Reuter, Fabian Dankert, Carsten Donsbach, Carsten von Hänisch
      First page: 11
      Abstract: Mismatched complexes of the alkali metals cations Li+ and Na+ were synthesized from 1,2-disila[18]crown-6 (1 and 2) and of K+ from 1,2,4,5-tetrasila[18]crown-6 (4). In these alkali metal complexes, not all crown ether O atoms participate in the coordination, which depicts the coordination ability of the C-, Si/C-, and Si-bonded O atoms. Furthermore, the inverse case—the coordination of the large Ba2+ ion by the relatively small ligand 1,2-disila[15]crown-5—was investigated, yielding the dinuclear complex 5. This structure represents a first outlook on sandwich complexes based on hybrid crown ethers.
      PubDate: 2017-02-09
      DOI: 10.3390/inorganics5010011
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 12: A Cancer Stem Cell Potent
           Cobalt(III)–Cyclam Complex Bearing Two Tolfenamic Acid Moieties

    • Authors: Paul Cressey, Arvin Eskandari, Kogularamanan Suntharalingam
      First page: 12
      Abstract: Cancer stem cells (CSCs) are thought to be responsible for cancer relapse. CSCs are a subtype of cancer cells with the ability to differentiate, self-renew, and form secondary or tertiary tumors. Current cancer treatments—including chemotherapy, radiation, and surgery—effectively remove bulk cancer cells but are unable to eliminate CSCs. Here, we present the synthesis, characterization, and anti-CSC properties of a cobalt(III)–cyclam complex bearing two tolfenamic acid moieties, 3. Notably, 3 displays sub-micromolar potency towards breast CSCs and bulk breast cancer cells. Detailed mechanistic studies show that 3 is taken up readily by breast CSCs, enters the nucleus, causes DNA damage, and induces caspase-dependent apoptosis. Furthermore, 3 inhibits cyclooxygenase-2 (COX-2) expression in CSCs. The mechanism of action of 3 is similar to that of a naproxen-appended cobalt(III)–cyclam complex, 1 recently reported by our group. The advantage of 3 over 1 is that it has the potential to remove whole tumor populations (bulk cancer cells and CSCs) with a single dose.
      PubDate: 2017-02-09
      DOI: 10.3390/inorganics5010012
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 13: K+···Cπ and K+···F Non-Covalent
           Interactions in π-Functionalized Potassium Fluoroalkoxides

    • Authors: Sorin-Claudiu Roşca, Hanieh Roueindeji, Vincent Dorcet, Thierry Roisnel, Jean-François Carpentier, Yann Sarazin
      First page: 13
      Abstract: Secondary interactions stabilize coordinatively demanding complexes of s-block metals [...]
      PubDate: 2017-03-07
      DOI: 10.3390/inorganics5010013
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 14: Light to Hydrogen: Photocatalytic Hydrogen
           Generation from Water with Molecularly-Defined Iron Complexes

    • Authors: Henrik Junge, Nils Rockstroh, Steffen Fischer, Angelika Brückner, Ralf Ludwig, Stefan Lochbrunner, Oliver Kühn, Matthias Beller
      First page: 14
      Abstract: Photocatalytic hydrogen generation is considered to be attractive due to its combination of solar energy conversion and storage. Currently-used systems are either based on homogeneous or on heterogeneous materials, which possess a light harvesting and a catalytic subunit. The subject of this review is a brief summary of homogeneous proton reduction systems using sacrificial agents with special emphasis on non-noble metal systems applying convenient iron(0) sources. Iridium photosensitizers, which were proven to have high quantum yields of up to 48% (415 nm), have been employed, as well as copper photosensitizers. In both cases, the addition or presence of a phosphine led to the transformation of the iron precursor with subsequently increased activities. Reaction pathways were investigated by photoluminescence, electron paramagnetic resonance (EPR), Raman, FTIR and mass spectroscopy, as well as time-dependent DFT-calculations. In the future, this knowledge will set the basis to design photo(electro)chemical devices with tailored electron transfer cascades and without the need for sacrificial agents.
      PubDate: 2017-03-09
      DOI: 10.3390/inorganics5010014
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 15: Synthesis and Catalytic Applications of
           Non-Metal Doped Mesoporous Titania

    • Authors: Syed Islam, Suraj Nagpure, Doo Kim, Stephen Rankin
      First page: 15
      Abstract: Mesoporous titania (mp-TiO2) has drawn tremendous attention for a diverse set of applications due to its high surface area, interfacial structure, and tunable combination of pore size, pore orientation, wall thickness, and pore connectivity. Its pore structure facilitates rapid diffusion of reactants and charge carriers to the photocatalytically active interface of TiO2. However, because the large band gap of TiO2 limits its ability to utilize visible light, non-metal doping has been extensively studied to tune the energy levels of TiO2. While first-principles calculations support the efficacy of this approach, it is challenging to efficiently introduce active non-metal dopants into the lattice of TiO2. This review surveys recent advances in the preparation of mp-TiO2 and their doping with non-metal atoms. Different doping strategies and dopant sources are discussed. Further, co-doping with combinations of non-metal dopants are discussed as strategies to reduce the band gap, improve photogenerated charge separation, and enhance visible light absorption. The improvements resulting from each doping strategy are discussed in light of potential changes in mesoporous architecture, dopant composition and chemical state, extent of band gap reduction, and improvement in photocatalytic activities. Finally, potential applications of non-metal-doped mp-TiO2 are explored in water splitting, CO2 reduction, and environmental remediation with visible light.
      PubDate: 2017-03-11
      DOI: 10.3390/inorganics5010015
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 16: On Mineral Retrosynthesis of a Complex
           Biogenic Scaffold

    • Authors: Ashit Rao, José Arias, Helmut Cölfen
      First page: 16
      Abstract: Synergistic relations between organic molecules and mineral precursors regulate biogenic mineralization. Given the remarkable material properties of the egg shell as a biogenic ceramic, it serves as an important model to elucidate biomineral growth. With established roles of complex anionic biopolymers and a heterogeneous organic scaffold in egg shell mineralization, the present study explores the regulation over mineralization attained by applying synthetic polymeric counterparts (polyethylene glycol, poly(acrylic acid), poly(aspartic acid) and poly(4-styrenesulfonic acid-co-maleic acid)) as additives during remineralization of decalcified eggshell membranes. By applying Mg2+ ions as a co-additive species, mineral retrosynthesis is achieved in a manner that modulates the polymorph and structure of mineral products. Notable features of the mineralization process include distinct local wettability of the biogenic organic scaffold by mineral precursors and mineralization-induced membrane actuation. Overall, the form, structure and polymorph of the mineralization products are synergistically affected by the additive and the content of Mg2+ ions. We also revisit the physicochemical nature of the biomineral scaffold and demonstrate the distinct spatial distribution of anionic biomolecules associated with the scaffold-mineral interface, as well as highlight the hydrogel-like properties of mammillae-associated macromolecules.
      PubDate: 2017-03-15
      DOI: 10.3390/inorganics5010016
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 17: Kudos and Renaissance of s-Block Metal

    • Authors: Sven Krieck, Matthias Westerhausen
      First page: 17
      Abstract: In recent years, the organometallic and coordination chemistry of the alkali and alkaline earth metals has experienced tremendous progress to tackle the needs of today’s society. Enhanced ecological awareness and global availability favor research on the chemistry of the essential s-block metals. Nowadays, the s-block metals are conquering new chemical fields based on sophisticated theoretical and preparative achievements. Recent investigations show a huge impact of the s-block elements on stoichiometric and catalytic processes.
      PubDate: 2017-03-21
      DOI: 10.3390/inorganics5010017
      Issue No: Vol. 5, No. 1 (2017)
  • Inorganics, Vol. 5, Pages 1: Modification of Deposited, Size-Selected MoS2
           Nanoclusters by Sulphur Addition: An Aberration-Corrected STEM Study

    • Authors: Yubiao Niu, Sung Park, Richard Palmer
      First page: 1
      Abstract: Molybdenum disulphide (MoS2) is an earth-abundant material which has several industrial applications and is considered a candidate for platinum replacement in electrochemistry. Size-selected MoS2 nanoclusters were synthesised in the gas phase using a magnetron sputtering, gas condensation cluster beam source with a lateral time-of-flight mass selector. Most of the deposited MoS2 nanoclusters, analysed by an aberration-corrected scanning transmission electron microscope (STEM) in high-angle annular dark field (HAADF) mode, showed poorly ordered layer structures with an average diameter of 5.5 nm. By annealing and the addition of sulphur to the clusters (by sublimation) in the cluster source, the clusters were transformed into larger, crystalline structures. Annealing alone did not lead to crystallization, only to a cluster size increase by decomposition and coalescence of the primary clusters. Sulphur addition alone led to a partially crystalline structure without a significant change in the size. Thus, both annealing and sulphur addition processes were needed to obtain highly crystalline MoS2 nanoclusters.
      PubDate: 2016-12-22
      DOI: 10.3390/inorganics5010001
      Issue No: Vol. 5, No. 1 (2016)
  • Inorganics, Vol. 5, Pages 2: The A-Type Ln4N2S3 Series: New Nitride
           Sulfides of the Light Lanthanoids (Ln = Ce–Nd)

    • Authors: Falk Lissner, Thomas Schleid
      First page: 2
      Abstract: The reaction of lanthanoid metal powders (Ln) with sulfur and cesium azide (CsN3) as a nitrogen source in the presence of lanthanoid tribromides (LnBr3) yields lanthanoid nitride sulfides with the composition Ln4N2S3 (Ln = Ce–Nd) when appropriate molar ratios of the starting material are used. Additional cesium bromide (CsBr) as a flux secures quantitative conversion (7 days) at 900 °C in evacuated silica tubes as well as the formation of black single crystals. All compounds crystallize isotypically with the orthorhombic crystal structure of La4N2S3 (Pnnm, Z = 2) and their structures were determined from single-crystal X-ray diffraction data (Ce4N2S3: a = 644.31(4), b = 1554.13(9), c = 404.20(3) pm; Pr4N2S3: a = 641.23(4), b = 1542.37(9), c = 400.18(3) pm; Nd4N2S3: a = 635.19(4), b = 1536.98(9), c = 397.85(3) pm). Compared to La4N2S3 the a-axes do not fulfill the expectation of the lanthanide contraction. The main feature of the crystal structure comprises N3−-centered (Ln3+)4 tetrahedra arranging as pairs [N2Ln6]12+ of edge-shared [NLn4]9+ units, which are further connected via four vertices to form double chains ∞ 1{([NLn4/2]2)6+}. Bundled along [001] like a hexagonal rod packing, they are held together by two crystallographically different S2− anions. Two compounds of a second modification (B-type La4N2S3 and Pr4N2S3) will also be presented and discussed for comparison.
      PubDate: 2016-12-23
      DOI: 10.3390/inorganics5010002
      Issue No: Vol. 5, No. 1 (2016)
  • Inorganics, Vol. 4, Pages 28: The Role of Anisotropic Exchange in Single
           Molecule Magnets: A CASSCF/NEVPT2 Study of the Fe4 SMM Building Block
           [Fe2(OCH3)2(dbm)4] Dimer

    • Authors: Alessandro Lunghi, Federico Totti
      First page: 28
      Abstract: The rationalisation of single molecule magnets’ (SMMs) magnetic properties by quantum mechanical approaches represents a major task in the field of the Molecular Magnetism. The fundamental interpretative key of molecular magnetism is the phenomenological Spin Hamiltonian and the understanding of the role of its different terms by electronic structure calculations is expected to steer the rational design of new and more performing SMMs. This paper deals with the ab initio calculation of isotropic and anisotropic exchange contributions in the Fe(III) dimer [Fe 2 (OCH 3 ) 2 (dbm) 4 ]. This system represents the building block of one of the most studied Single Molecule Magnets ([Fe 4 RC(CH 2 O) 3 ) 2 (dpm) 6 ] where R can be an aliphatic chain or a phenyl group just to name the most common functionalization groups) and its relatively reduced size allows the use of a high computational level of theory. Calculations were performed using CASSCF and NEVPT2 approaches on the X-ray geometry as assessment of the computational protocol, which has then be used to evinced the importance of the outer coordination shell nature through organic ligand modelization. Magneto-structural correlations as function of internal degrees of freedom for isotropic and anisotropic exchange contributions are also presented, outlining, for the first time, the extremely rapidly changing nature of the anisotropic exchange coupling.
      PubDate: 2016-09-22
      DOI: 10.3390/inorganics4040028
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 29: Synthesis and Structure Determination of the
           Quaternary Zinc Nitride Halides Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0
           < y < 1)

    • Authors: Yanqing Li, Xiaohui Liu, Richard Dronskowski
      First page: 29
      Abstract: The quaternary series Zn2NCl1−yBry and Zn2NBr1−yIy were synthesized from solid-liquid reactions between zinc nitride and the respective zinc halides in closed ampoules, and the evolution of their crystal structures was investigated by single-crystal and powder X-ray diffraction. Zn2NX1−yX′y (X, X′ = Cl, Br, I) adopts the anti-β-NaFeO2 motif in which each nitride ion is tetrahedrally coordinated by four zinc cations, and the halide anions are located in the voids of the skeleton formed by corner-sharing [NZn4] tetrahedra. While Zn2NCl1−yBry crystallizes in the acentric orthorhombic space group Pna21 (No. 33), isotypic to Zn2NX (X = Cl, Br), the structure of Zn2NBr1−yIy is a function of the iodide concentration, namely, Zn2NBr (Pna21) for low iodine content and Zn2NI (Pnma) for higher (y ≥ 0.38).
      PubDate: 2016-09-29
      DOI: 10.3390/inorganics4040029
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 30: η1:η2-P-Pyrazolylphosphaalkene
           Complexes of Ruthenium(0)

    • Authors: Victoria Greenacre, Ian Crossley
      First page: 30
      Abstract: An extended range of novel ruthenium phosphaalkene complexes of the type [Ru{η1-N:η2-P,C-P(pz′)=CH(SiMe2R)}(CO)(PPh3)2] (R = Tol, C6H4CF3-p; pz′ = pzMe2, pzCF3, pzMe,CF3; R = Me, C6H4CF3-p; pz′ = pzPh) have been prepared from the respective ruthenaphosphaalkenyls [Ru{P=CH(SiMe2R)}Cl(CO)(PPh3)2] upon treatment with Lipz′. Where R = C6H4CF3-p and pz′ = pzMe2 the complex is characterized by single crystal X-ray diffraction, only the second example of such species being structurally characterized. This indicates enhanced pyramidalisation of the alkenic carbon center when compared with precedent data (R = Me, pz′ = pz) implying an enhanced Ru→π*PC contribution, which can be correlated with the greater donor power of pzMe2. This is similarly reflected in spectroscopic data that reveal significant influence of the pyrazolyl substituents upon the phosphaalkene, stronger donors imparting significantly enhanced shielding to phosphorus; in contrast, a much lesser influence if noted for the silyl substituents.
      PubDate: 2016-09-30
      DOI: 10.3390/inorganics4040030
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 31: Rare Earth and Actinide Complexes

    • Authors: Stephen Mansell, Stephen Liddle
      First page: 31
      Abstract: The rare earth metals (scandium, yttrium, lanthanum and the subsequent 4f elements) and actinides (actinium and the 5f elements) are vital components of our technology-dominated society.[...]
      PubDate: 2016-10-14
      DOI: 10.3390/inorganics4040031
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 32: Direct Catalytic Conversion of Cellulose to
           5-Hydroxymethylfurfural Using Ionic Liquids

    • Authors: Sanan Eminov, Paraskevi Filippousi, Agnieszka Brandt, James Wilton-Ely, Jason Hallett
      First page: 32
      Abstract: Cellulose is the single largest component of lignocellulosic biomass and is an attractive feedstock for a wide variety of renewable platform chemicals and biofuels, providing an alternative to petrochemicals and petrofuels. This potential is currently limited by the existing methods of transforming this poorly soluble polymer into useful chemical building blocks, such as 5-hydroxymethylfurfural (HMF). Ionic liquids have been used successfully to separate cellulose from the other components of lignocellulosic biomass and so the use of the same medium for the challenging transformation of cellulose into HMF would be highly attractive for the development of the biorefinery concept. In this report, ionic liquids based on 1-butyl-3-methylimidazolium cations [C4C1im]+ with Lewis basic (X = Cl−) and Brønsted acidic (X = HSO4−) anions were used to investigate the direct catalytic transformation of cellulose to HMF. Variables probed included the composition of the ionic liquid medium, the metal catalyst, and the reaction conditions (temperature, substrate concentration). Lowering the cellulose loading and optimising the temperature achieved a 58% HMF yield after only one hour at 150 °C using a 7 mol % loading of the CrCl3 catalyst. This compares favourably with current literature procedures requiring much longer reactions times or approaches that are difficult to scale such as microwave irradiation.
      PubDate: 2016-10-20
      DOI: 10.3390/inorganics4040032
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 33: Water-Soluble Cellulose Derivatives Are
           Sustainable Additives for Biomimetic Calcium Phosphate Mineralization

    • Authors: Andreas Taubert, Christian Balischewski, Doreen Hentrich, Thomas Elschner, Sascha Eidner, Christina Günter, Karsten Behrens, Thomas Heinze
      First page: 33
      Abstract: The effect of cellulose-based polyelectrolytes on biomimetic calcium phosphate mineralization is described. Three cellulose derivatives, a polyanion, a polycation, and a polyzwitterion were used as additives. Scanning electron microscopy, X-ray diffraction, IR and Raman spectroscopy show that, depending on the composition of the starting solution, hydroxyapatite or brushite precipitates form. Infrared and Raman spectroscopy also show that significant amounts of nitrate ions are incorporated in the precipitates. Energy dispersive X-ray spectroscopy shows that the Ca/P ratio varies throughout the samples and resembles that of other bioinspired calcium phosphate hybrid materials. Elemental analysis shows that the carbon (i.e., polymer) contents reach 10% in some samples, clearly illustrating the formation of a true hybrid material. Overall, the data indicate that a higher polymer concentration in the reaction mixture favors the formation of polymer-enriched materials, while lower polymer concentrations or high precursor concentrations favor the formation of products that are closely related to the control samples precipitated in the absence of polymer. The results thus highlight the potential of (water-soluble) cellulose derivatives for the synthesis and design of bioinspired and bio-based hybrid materials.
      PubDate: 2016-10-24
      DOI: 10.3390/inorganics4040033
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 34: Metal-Free Reduction of Phosphine Oxides
           Using Polymethylhydrosiloxane

    • Authors: Emmanuel Nicolas, Antonella Guerriero, Volodymyr Lyaskovskyy, Maurizio Peruzzini, Koop Lammertsma, Luca Gonsalvi, J. Slootweg
      First page: 34
      Abstract: A simple protocol is presented here for the use of inexpensive polymethylhydrosiloxane (PMHS), a waste product of the silicon industry, as stoichiometric reducing agent for phosphine oxides to phosphines, a highly desirable reaction to recover P-based ligands from their spent form. The reactions were studied by screening parameters, such as substrate to reductant ratio, temperature and reaction time, achieving good conversions and selectivities.
      PubDate: 2016-11-03
      DOI: 10.3390/inorganics4040034
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 35: In Situ Studies and Magnetic Properties of
           the Cmcm Polymorph of LiCoPO4 with a Hierarchical Dumbbell-Like Morphology
           Synthesized by Easy Single-Step Polyol Synthesis

    • Authors: Carlos Alarcón-Suesca, Jennifer Ludwig, Viktor Hlukhyy, Christoph Stinner, Tom Nilges
      First page: 35
      Abstract: LiCoPO4 (LCP) exists in three different structural modifications: LCP-Pnma (olivine structure), LCP-Pn21a (KNiPO4 structure type), and LCP-Cmcm (Na2CrO4 structure type). The synthesis of the LCP-Cmcm polymorph has been reported via high pressure/temperature solid-state methods and by microwave-assisted solvothermal synthesis. Phase transitions from both LCP-Pn21a and LCP-Cmcm to LCP-Pnma upon heating indicates a metastable behavior. However, a precise study of the structural changes during the heating process and the magnetic properties of LCP-Cmcm are hitherto unknown. Herein, we present the synthesis and characterization of LCP-Cmcm via a rapid and facile soft-chemistry approach using two different kinetically controlled pathways, solvothermal and polyol syntheses, both of which only require relatively low temperatures (~200 °C). Additionally, by polyol, method a dumbbell-like morphology is obtained without the use of any additional surfactant or template. A temperature-dependent in situ powder XRD shows a transition from LCP-Cmcm at room temperature to LCP-Pnma and finally to LCP-Pn21a at 575 and 725 °C, respectively. In addition to that, the determination of the magnetic susceptibility as a function of temperature indicates a long-range antiferromagnetic order below TN = 11 K at 10 kOe and 9.1 K at 25 kOe. The magnetization curves suggests the presence of a metamagnetic transition.
      PubDate: 2016-11-17
      DOI: 10.3390/inorganics4040035
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 36: PP-Rotation, P-Inversion and Metathesis in
           Diphosphines Studied by DFT Calculations: Comments on Some Literature

    • Authors: Adam Molloy, Goar Sánchez-Sanz, Declan Gilheany
      First page: 36
      Abstract: The potential energy surface for internal rotation about the phosphorus–phosphorus bond was calculated at the PCMDCM/B3LYP/6-311++G(d,p) computational level for a set of eight symmetrical, unsymmetrical and P-stereogenic diphosphines; H4P2, Me4P2, (CF3)4P2, Ph4P2, Me2P–P(CF3)2, Me2P–PPh2, and the meso- and dl-isomers of Me(CF3)P–PMe(CF3) and MePhP–PMePh. Certain trends in the data were elucidated and compared with conflicting data from the literature regarding the relative population of anti and gauche rotational isomers. The pyramidal inversion barriers (stereomutation barriers in P-stereogenic cases) for the same set of diphosphines was estimated through the inversion transition states and also compared to literature values. Finally, the Me4P2 + (CF3)4P2 → 2Me2(CF3)2P2 metathesis reaction was also explored to evaluate its feasibility versus inversion. The finding of larger barriers in the metathesis than in the inversion rules in favour of an inversion mechanism for the stereomutation of P-stereogenic diphosphines.
      PubDate: 2016-11-18
      DOI: 10.3390/inorganics4040036
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 37: Structural Classification of
           Quasi-One-Dimensional Ternary Nitrides

    • Authors: David Headspith, Maria Francesconi
      First page: 37
      Abstract: This review focuses on the crystal structural features of ternary (mixed-metal) quasi-one-dimensional nitrides i.e., nitrides containing (cation-N3−) coordination polyhedra sharing either corners, edges, or faces, arranged in linear chains, and intercalated by a counter ion. The current relevance of these nitrides, and of quasi-one-dimensional compounds in general, lies in the fact that they are closely related to the pure one-dimensional systems (i.e., nanowires), which are vastly researched for their amazing properties closely related to their low dimensionality. A number of these properties were firstly discovered in quasi-one-dimensional compounds, highlighting the importance of expanding knowledge and research in this area. Furthermore, unlike oxides, nitrides and other non-oxide compounds are less developed, hence more difficult to categorise into structural classes that can then be related to other classes of compounds, leading to a fuller picture of structure–properties relationship. Within this context, this review aims to categorise and describe a number of ternary (mixed-metal) quasi-one-dimensional nitrides according to their structural features, specifically, the polyhedra forming the one-dimensional chains.
      PubDate: 2016-11-30
      DOI: 10.3390/inorganics4040037
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 38: Steroid-Functionalized Titanocenes: Docking
           Studies with Estrogen Receptor Alpha

    • Authors: Li Gao, Wilson Maldonado, Xiomara Narváez-Pita, José Carmona-Negrón, Jesus Olivero-Verbel, Enrique Meléndez
      First page: 38
      Abstract: Estrogen receptor alpha (ERα) is a transcription factor that is activated by hormones, with 17β-estradiol being its most active agonist endogenous ligand. ERα is also activated or inactivated by exogenous ligands. ER is overexpressed in hormone-dependent breast cancer, and one of the treatments for this type of cancer is the use of an ER antagonist to halt cell proliferation. We have previously reported four steroid-functionalized titanocenes: pregnenolone, dehydroepiandrosterone (DHEA), trans-androsterone, and androsterone. These steroids have hormonal activity as well as moderate antiproliferative activity, thus these steroids could act as vectors for the titanocene dichloride to target hormone-dependent cancers. Also, these steroids could increase the antiproliferative activity of the resulting titanocenes based on synergism. In order to elucidate which factors contribute to the enhanced antiproliferative activity of these steroid-functionalized titanocenes, we performed docking studies between ERα and the titanocenes and the steroids. The binding affinities and type of bonding interactions of the steroid-functionalized titanocenes with ERα are herein discussed.
      PubDate: 2016-11-30
      DOI: 10.3390/inorganics4040038
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 39: Reduction of Bromo- and
           Iodo-2,6-bis(diphenylphosphanylmethyl)benzene with Magnesium and Calcium

    • Authors: Alexander Koch, Sven Krieck, Helmar Görls, Matthias Westerhausen
      First page: 39
      Abstract: Arylmagnesium and -calcium reagents are easily accessible; however, ether degradation processes limit storability, especially of the calcium-based heavy Grignard reagents. Ortho-bound substituents with phosphanyl donor sites usually block available coordination sites and stabilize such complexes. The reaction of bromo-2,6-bis(diphenylphosphanylmethyl)benzene (1a) with magnesium in tetrahydrofuran yields [Mg{C6H3-2,6-(CH2PPh2)2}2] (2) after recrystallization from 1,2-dimethoxyethane. However, the similarly performed reduction of bromo- (1a) and iodo-2,6-bis(diphenylphosphanylmethyl)benzene (1b) with calcium leads to ether cleavage and subsequent degradation products. α-Deprotonation of tetrahydrofuran (THF) yields 1,3-bis(diphenylphosphanylmethyl)benzene. Furthermore, the insoluble THF adducts of dimeric calcium diphenylphosphinate halides, [(thf)3Ca(X)(µ-O2PPh2)]2 [X = Br (3a), I (3b)], precipitate verifying ether decomposition and cleavage of P–C bonds. Ether adducts of calcium halides (such as [(dme)2(thf)CaBr2] (4)) form, supporting the initial Grignard reaction and a subsequent Schlenk-type dismutation reaction.
      PubDate: 2016-12-01
      DOI: 10.3390/inorganics4040039
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 40: Synthesis and Characterization of a
           Sulfonyl- and Iminophosphoryl-Functionalized Methanide and Methandiide

    • Authors: Kai-Stephan Feichtner, Viktoria Gessner
      First page: 40
      Abstract: The synthesis of [H2C(PPh2=NSiMe3)(SO2Ph)] (1) and its mono- and dimetalation are reported. Due to the strong anion-stabilizing abilities of the iminophosphoryl and the sulfonyl group monometalation to 1-K and dimetalation to 1-Li2 proceed smoothly with potassium hydride and methyllithium, respectively. Both compounds could be isolated in high yields and were characterized by NMR spectroscopy as well as XRD analysis. The methanide 1-K forms a coordination polymer in the solid state, while in case of the methandiide a tetrameric structure is observed. The latter features an unusual structural motif consisting of two (SO2Li)2 eight-membered rings, which are connected with each other via the methandiide carbon atoms and additional lithium atoms. With increasing metalation a contraction of the P–C–S linkage is observed, which is well in line with the increased charge at the central carbon atom and involved electrostatic interactions.
      PubDate: 2016-12-02
      DOI: 10.3390/inorganics4040040
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 41: Ammonothermal Synthesis and Crystal
           Structures of Diamminetriamidodizinc Chloride [Zn2(NH3)2(NH2)3]Cl and
           Diamminemonoamidozinc Bromide [Zn(NH3)2(NH2)]Br

    • Authors: Theresia Richter, Sabine Strobel, Nicolas Alt, Eberhard Schlücker, Rainer Niewa
      First page: 41
      Abstract: The treatment of excess zinc in the presence of ammonium chloride under ammonothermal conditions of 873 K and 97 MPa leads to diamminetriamidodizinc chloride [Zn2(NH3)2(NH2)3]Cl with a two-dimensionally μ-amido-interconnected substructure. Similar reaction conditions using ammonium bromide instead of the chloride (773 K, 230 MPa) result in diamminemonoamidozinc bromide [Zn(NH3)2(NH2)]Br with one-dimensional infinite μ-amido-bridged chains. Both compounds were obtained as colorless, very moisture sensitive crystals. Crystal structures and hydrogen bond schemes are analyzed. Raman spectroscopic data of the chloride are reported.
      PubDate: 2016-12-09
      DOI: 10.3390/inorganics4040041
      Issue No: Vol. 4, No. 4 (2016)
  • Inorganics, Vol. 4, Pages 42: Single Crystal Growth and Anisotropic
           Magnetic Properties of Li2Sr[Li1 − xFexN]2

    • Authors: Peter Höhn, Tanita Ballé, Manuel Fix, Yurii Prots, Anton Jesche
      First page: 42
      Abstract: Up to now, investigation of physical properties of ternary and higher nitridometalates has been severely hampered by challenges concerning phase purity and crystal size. Employing a modified lithium flux technique, we are now able to prepare sufficiently large single crystals of the highly air and moisture sensitive nitridoferrate Li 2 Sr[Li 1 − x Fe x N] 2 for anisotropic magnetization measurements. The magnetic properties are most remarkable: large anisotropy and coercivity fields of 7 Tesla at T = 2 K indicate a significant orbital contribution to the magnetic moment of iron. Altogether, the novel growth method opens a route towards interesting phases in the comparatively recent research field of nitridometalates and should be applicable to various other materials.
      PubDate: 2016-12-21
      DOI: 10.3390/inorganics4040042
      Issue No: Vol. 4, No. 4 (2016)
  • 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

    • 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 &gt; Cu &gt; 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

    • 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 &gt; S &gt; 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

    • Authors: Daniela Gerlach, Erica Brendler, Jörg Wagler
      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

    • Authors: Anne Galarneau, Zakaria Abid, Bilel Said, Youcef Didi, Katarzyna Szymanska, Andrzej Jarzębski, Franck Tancret, Hadj Hamaizi, Abdelkader Bengueddach, Francesco Di Renzo, Francois Fajula
      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

    • Authors: Frédéric Lefebvre
      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

    • Authors: Nerea Andino, Beñat Artetxe, Santiago Reinoso, Pablo Vitoria, Leire San Felices, Jose Martínez, Fernando López Arbeloa, Juan Gutiérrez-Zorrilla
      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:

    • 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

    • 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 &lt;&lt; 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

    • 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

    • Authors: Jérémy Dhainaut, Sylvain Deville, Idris Amirouche, Michaela Klotz
      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)
School of Mathematical and Computer Sciences
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