European Journal of Inorganic Chemistry

Cover image for Vol. 2015 Issue 3

Early View (Online Version of Record published before inclusion in an issue)

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.965

ISI Journal Citation Reports © Ranking: 2013: 10/45 (Chemistry Inorganic & Nuclear)

Online ISSN: 1099-0682

Associated Title(s): Angewandte Chemie International Edition, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemCatChem, Zeitschrift für anorganische und allgemeine Chemie

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  1. 1 - 69
  1. Full Papers

    1. Heterometallic Catalysts

      A Metalloligand Appended with Thiazole Rings: Heterometallic {Co3+–Zn2+} and {Co3+–Cd2+} Complexes and Their Hetero­geneous Catalytic Applications

      Deepak Bansal, Geeta Hundal and Rajeev Gupta

      Article first published online: 27 JAN 2015 | DOI: 10.1002/ejic.201403072

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      A Co3+-based metalloligand with appended thiazole rings is used to synthesize heterometallic {Co3+–Zn2+} and {Co3+–Cd2+} complexes. These complexes function as reusable heterogeneous catalysts for ring-opening, cyanation, and Knoevenagel condensation reactions. The results illustrate the importance of the microenvironment of catalytic metal centers to potentially enhance substrate interactions.

    2. Carbon Dioxide Sorption

      Intercalative Ion-Exchange Route to Amino Acid Layered Double Hydroxide Nanohybrids and Their Sorption Properties

      Goeun Choi, Jae-Hun Yang, Ga-Young Park, Ajayan Vinu, Ahmad Elzatahry, Chul Hyun Yo and Jin-Ho Choy

      Article first published online: 27 JAN 2015 | DOI: 10.1002/ejic.201403115

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      The CO2 uptake capacity in the present study is influenced not only by the specific surface area but also by the number of reactive amine sites in the pore, as the amine groups of amino acids interact with adsorbed CO2 molecules to form carbamates by a zwitterionic mechanism even at low temperature.

  2. Short Communications

    1. Luminescent Thermometers

      Lanthanide Complex Hybrid System for Fluorescent Sensing as Thermometer

      Xiang Shen, Ye Lu and Bing Yan

      Article first published online: 27 JAN 2015 | DOI: 10.1002/ejic.201403106

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      A mixed lanthanide complex was synthesized hydrothermally with two organic ligands, adenine and biphenyl-4,4′-dicarboxylic acid, and is formulated as Ad/Tb0.999Eu0.001/BPDC (Ad: adeninate, BPDC: biphenyl-4,4′-dicarboxylate). It can be used as a ratiometric luminescent thermometer on the basis of the energy transfer from Tb3+ to Eu3+, whose color changes from green–yellow to red from 100 to 300 K.

    2. Heterotrinuclear Confacial Trioctahedron

      The First Heterotrinuclear Confacial Trioctahedron NiIITiIVCrIII: Rational Modular Assembly and Cooperative Effects

      Bodo Sonnenburg, Ioannis Liratzis, Anja Stammler, Hartmut Bögge and Thorsten Glaser

      Article first published online: 27 JAN 2015 | DOI: 10.1002/ejic.201403191

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      The ligand H6ioan allows the synthesis of the first confacial trioctahedron [(ioan)NiTiCrCl3] with three different metal ions.

  3. Full Papers

    1. Energetic Materials

      5-Ferrocenyl-1H-tetrazole-Derived Transition-Metal Complexes: Synthesis, Crystal Structures and Catalytic Effects on the Thermal Decomposition of the Main Components of Solid Propellants

      Chunyan Wang, Jizhen Li, Xuezhong Fan, Fengqi Zhao, Weiqiang Zhang, Guofang Zhang and Ziwei Gao

      Article first published online: 26 JAN 2015 | DOI: 10.1002/ejic.201402894

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      Eight 5-ferrocenyl-1H-tetrazole-derived transition-metal complexes have been synthesized and characterized by single-crystal X-ray diffraction. The new compounds exhibit high thermal stability and large catalytic effects on the thermal degradation of ammonium perchlorate and 1,3,5-trinitro-1,3,5-triazacyclohexane.

    2. Iron Nitrosyl Chemistry

      Tracing the Iron Nitrosyl Complex [Fe(2,2′-bipyridine)(CN)3(NO)]

      Ana Foi, Florencia Di Salvo, Fabio Doctorovich, Tapashi G. Roy, Kathrin Stirnat, Christian Biewer and Axel Klein

      Article first published online: 23 JAN 2015 | DOI: 10.1002/ejic.201403145

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      The previously reported complex [Ph4P][Fe(bpy)(CN)3(NO)] (bpy = 2,2′-bipyridine) was synthesised and a detailed structural (single-crystal XRD), (spectro)electrochemical and spectroscopic insight is provided that adds perfectly to the previous electrochemical characterisation.

  4. Short Communications

    1. Non-Equilibrium Phases

      Crystalline Non-Equilibrium Phase of a Cobalt(II) Complex with Tridentate Ligands

      Christoph Förster, Tatiana E. Gorelik, Ute Kolb, Vadim Ksenofontov and Katja Heinze

      Article first published online: 23 JAN 2015 | DOI: 10.1002/ejic.201403200

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      Rapid precipitation yields microcrystals of the so far elusive kinetic intermediate of [Co(ddpd)2](BF4)2 (ddpd = N,N′-dimethyl-N,N′-dipyridine-2-yl-pyridine-2,6-diamine). Its solid-state structure has been determined from electron diffraction data.

  5. Full Papers

    1. Hydrogenation with MOFs

      Metal–Organic Frameworks Based on Alkaline Earth Metals – Hydrothermal Synthesis, X-ray Structures, Gas Adsorption, and Heterogeneously Catalyzed Hydrogenation Reactions

      Debraj Saha, Tanmoy Maity and Subratanath Koner

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejic.201403149

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      Compounds generated by the thermal dehydration of Ca- and Sr-based metal–organic frameworks (MOFs) possess pores with open unsaturated metal sites and exhibit excellent adsorption capacity for N2, H2, and CO2 at low pressure. The calcined MOFs catalyze the hydrogenation of olefins under mild heterogeneous conditions (60 °C, 1 atm H2).

    2. Scandium Compounds

      Three Scandium Compounds with Unsaturated Coordinative Metal Sites – Structures and Catalysis

      Liying Zhang, Li Wang, PengCheng Wang, Tianyou Song, Da Li, Xiaobo Chen, Yong Fan and Jianing Xu

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejic.201402740

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      Three scandium compounds have been prepared under solvothermal conditions. These new materials are stable in CH3CN and show good Lewis acid catalytic activity for cyanosilylation of aromatic aldehydes by virtue of their coordinative unsaturated metal sites. Over successive cycles, a small decrease in activity was observed for two of the catalysts.

    3. Rare Earth Silicate Apatites

      Crystallographic and Spectroscopic Investigations on Nine Metal–Rare-Earth Silicates with the Apatite Structure Type

      Maria Wierzbicka-Wieczorek, Martin Göckeritz, Uwe Kolitsch, Christoph Lenz and Gerald Giester

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejic.201403070

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      Nine metal–rare-earth silicates with the apatite structure type were synthesised by a high-temperature flux-growth technique. Their metaprism twist angle depends on the anions present in the crystal structure, and their photoluminescence properties could be useful for luminescent devices.

    4. Antimony Sulfides

      A Series of Noncentrosymmetric Antimony Sulfides Ln8Sb2S15 (Ln = La, Pr, Nd) – Syntheses, Crystal and Electronic Structures, and NLO Properties

      Hua-Jun Zhao and Liu-Jiang Zhou

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejic.201403074

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      A series of noncentrosymmetric antimony sulfides Ln8Sb2S15 (Ln = La, Pr, Nd) were prepared. Their structures contain discrete [SbS3]3– trigonal pyramids separated by the Ln3+ cations and S2– anions. The compound La8Sb2S15 shows second harmonic generation with intensities 1.2 times that of the commercially used IR NLO material AgGaS2.

    5. Mesoporous Ceria Nanoparticles

      Facile Preparation of Mn+-Doped (M = Cu, Co, Ni, Mn) Hierarchically Mesoporous CeO2 Nanoparticles with Enhanced Catalytic Activity for CO Oxidation

      Jingcai Zhang, Jinxin Guo, Wei Liu, Shuping Wang, Anran Xie, Xiufang Liu, Jun Wang and Yanzhao Yang

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejic.201403078

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      A series of transition-metal-doped (Cu, Co, Ni, Mn) hierarchically mesoporous CeO2 nanoparticles assembled from hollow nanocones were prepared through a simple solvothermal strategy. The doped ceria nanoparticles exhibit improved reduction behavior and enhanced catalytic activity for CO oxidation.

    6. Orthoperiodates

      The Orthoperiodates of Calcium, Strontium, and Barium

      Thorsten Hummel, Florian Salk, Markus Ströbele, David Enseling, Thomas Jüstel and H.-Jürgen Meyer

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejic.201403094

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      Orthoperiodates of calcium, strontium, and barium were prepared by solid-state reactions of metal iodides or metal iodates with oxygen in air. The reactions were investigated by using differential thermal analysis and thermogravimetric analysis. Luminescence properties of europium-doped samples are reported.

    7. Spin Crossover

      Discrete FeII Spin-Crossover Complexes of 2,2′-Dipyridylamino-Substituted s-Triazine Ligands with Phenoxo, Cyanophenoxo and Dibenzylamino Functionalities

      Hayley S. Scott, Tamsyn M. Ross, Wasinee Phonsri, Boujemaa Moubaraki, Guillaume Chastanet, Jean-François Létard, Stuart R. Batten and Keith S. Murray

      Article first published online: 20 JAN 2015 | DOI: 10.1002/ejic.201402972

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      New mononuclear spin-crossover compounds of type trans-[FeII(NCX)2(L)2]·solvent have been synthesised and structurally characterised. The L ligands are chelated to Fe by dipyridylamine groups and have aromatic substituents on the central triazine ring that influence cooperativity effects monitored by magnetic and light-induced excited-state spin trapping (LIESST) measurements.

  6. Short Communications

    1. Manganese Clusters

      A Mn6 Cluster inside a Mn10 Wheel: Characterization of a Mn16-Oximate Complex Resulting from a Tetrazole-2-pyridylketoneoximate Ligand

      Laura Alcazar, Mercè Font-Bardia and Albert Escuer

      Article first published online: 20 JAN 2015 | DOI: 10.1002/ejic.201403128

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      Tetrazole-2-pyridylketoneoximate, obtained by in situ cyclization of 2-pyridylcyanoximate and azide, was characterized in a Mn16 complex with an unprecedented topology formed by one hexanuclear {MnII2MnIII4} unit coordinated perpendicularly to a decametallic {MnII6MnIII2MnIV2} wheel.

  7. Microreviews

    1. Dinitrogen Activation

      Reactivity of Dinitrogen Bound to Mid- and Late-Transition-Metal Centers

      Nitesh Khoenkhoen, Bas de Bruin, Joost N. H. Reek and Wojciech I. Dzik

      Article first published online: 20 JAN 2015 | DOI: 10.1002/ejic.201403041

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      Mid- and late-transition metals are excellent platforms for enabling the reactivity of dinitrogen. This microreview gives an overview of the many reactions in which N2 is cleaved or forms new bonds with electrophiles or radicals. These reactions occur under ambient conditions, and some of them, such as the formation of ammonia or silylamines, are even catalytic.

  8. Full Papers

    1. Acceptorless Dehydrogenation

      Formation of Different Isomers of Phosphine–Imidazolyl and –Pyridyl Ruthenium(II) Complexes Affecting the Catalyst Activity in the Acceptorless Dehydrogenation of Alcohols

      Robert Langer, Alexander Gese, Donatas Gesevičius, Maximilian Jost, Bastian R. Langer, Felix Schneck, Alexander Venker and Weiqin Xu

      Article first published online: 19 JAN 2015 | DOI: 10.1002/ejic.201402970

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      Different ruthenium dichloride complexes with P,N ligands have been synthesized and compared in their activity in the acceptorless dehydrogenation of primary alcohols, thereby demonstrating that small changes in the ligand moiety have a strong impact on the relative stability of isomeric dihydride and dichloride complexes and thus on the catalytic activity.

    2. Bioactive Bi Complexes

      Homoleptic and Heteroleptic Bismuth(III) Thiazole–Thiolates and the Influence of Ring Substitution on Their Antibacterial and Antileishmanial Activity

      Ahmad Luqman, Victoria L. Blair, Rajini Brammananth, Paul K. Crellin, Ross L. Coppel, Lukasz Kedzierski and Philip C. Andrews

      Article first published online: 19 JAN 2015 | DOI: 10.1002/ejic.201402958

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      Thiazole-based bismuth(III) complexes, [BiPh(MBT)2]2 and [Bi(MBT)3]2, derived from 4-phenylthiazole-2-thiol, MBT(H), have been synthesised and structurally characterised; X-ray diffraction studies played a central role in structure elucidation efforts. [BiPh(MBT)2]2 is strongly active against common and multi-resistant bacteria, and against the Leishmania parasite.

    3. Actinide Pnictide Chalcogenides

      UPTe, ThPTe and U2PTe2O: Actinide Pnictide Chalcogenides with Diphosphide Anions

      Karoline Stolze, Anna Isaeva, Ulrich Schwarz and Thomas Doert

      Article first published online: 19 JAN 2015 | DOI: 10.1002/ejic.201402951

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      Single crystal structure investigations, Raman data and real-space bonding analysis unveil the presence of diphosphide anions in UPTe. For hitherto unknown ThPTe, X-ray powder data indicate an analogous structural pattern. The new compound U2PTe2O, a partially oxidised variant of UPTe, also contains layers of P2 anions in a parallel arrangement.

    4. White-Light-Emitting MOFs

      3D Microporous Lanthanide–Organic Frameworks Constructed from Left- and Right-Handed Helical Chains: Synthesis, Crystal Structure, and Tunable Photo­luminescence

      Rui Huo, Xia Li and Dou Ma

      Article first published online: 19 JAN 2015 | DOI: 10.1002/ejic.201403026

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      Lanthanide frameworks were assembled from 2,6-naphthalenedisulfonate and 1H-imidazo[4,5-f][1,10]-phenanthroline. They have 3D microporous structures constructed from left- and right-handed helical chains. The SmIII complex and the EuIII/TbIII-doped complex allowed the realization of luminescence tuning and white-light emission.

  9. Short Communications

    1. Theranostis Gd Agents

      Synthesis and Structure–Activity Relationships of Gadolinium Complexes of DO3A–Benzothiazole Conjugates as Potential Theranostic Agents

      Ki-Hye Jung, Sun-Hee Kang, Min-Kyoung Kang, Soyeon Kim, Hee-Kyung Kim, Yeoun-Hee Kim, Gang Ho Lee, Gyu-Bo Shim, Jae-Chang Jung, Yongmin Chang and Tae-Jeong Kim

      Article first published online: 15 JAN 2015 | DOI: 10.1002/ejic.201403123

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      The synthesis of DO3A derivatives of benzothiazole and their Gd complexes for use as single-molecule theranostic agents is reported. The complexes are tumor specific and are also intracellular, which enhances magnetic resonance images of cytosols and nuclei of various tumor cells. GdL3 reveals antiproliferative activities, as demonstrated by growth-inhibition and total-growth-inhibition values.

  10. Full Papers

    1. Dicationic Diborole Complexes

      Dicationic μ-Diborolyl Arene Triple-Decker Complexes [CpCo(μ-1,3-C3B2Me5)M(arene)]2+ (M = Rh, Ir; Cp = Cyclopentadienyl): Synthesis, Structures, Electrochemistry and Bonding

      Dmitry V. Muratov, Alexander S. Romanov, Dmitry A. Loginov, Maddalena Corsini, Fabrizia Fabrizi de Biani and Alexander R. Kudinov

      Article first published online: 15 JAN 2015 | DOI: 10.1002/ejic.201402927

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      The labile nitromethane solvates [CpCo(μ-1,3-C3B2Me5)M(MeNO2)3]2+ {generated from the bromide complexes [CpCo(μ-1,3-C3B2Me5)MBr2]2 (M = Rh, Ir; Cp = cyclopentadienyl) and AgBF4 in MeNO2} react with arenes to give triple-decker complexes [CpCo(μ-1,3-C3B2Me5)M(arene)]2+. X-ray diffraction, electrochemical techniques and DFT calculations were used for the characterization of the complexes obtained.

  11. Short Communications

    1. Bismuth Drugs

      The Unexpected Isolation of Bismuth Tris(carboxylate) Hydrates: Syntheses and Structures of [Bi(Hsal)3(H2O)] and [Bi(Hanth)3(H2O)] (H2sal = 2-OH-C6H4CO2H, Hanth = 2-NH2-C6H4CO2H)

      Ish Kumar, Phil Andrews and Kenton H. Whitmire

      Article first published online: 15 JAN 2015 | DOI: 10.1002/ejic.201403019

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      Treatment of BiPh3 with salicylic acid in xylene in the presence of air leads to the unexpected isolation of the tris(salicylato)bismuth(III) hydrate.

  12. Full Papers

    1. Cytotoxic Copper Complexes

      Transition Metal Complexes with 1-Adamantoyl Hydrazones – Cytotoxic Copper(II) Complexes of Tri- and Tetradentate Pyridine Chelators Containing an Adamantane Ring System

      Vukadin M. Leovac, Marko V. Rodić, Ljiljana S. Jovanović, Milan D. Joksović, Tatjana Stanojković, Miroslava Vujčić, Dušan Sladić, Violeta Marković and Ljiljana S. Vojinović-Ješić

      Article first published online: 15 JAN 2015 | DOI: 10.1002/ejic.201403050

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      Five CuII complexes with 2-acetylpyridine or di(2-pyridyl) ketone 1-adamantoyl hydrazones have been prepared and physicochemically characterized. All of the tested complexes exhibit strong cytotoxic activity and induce apoptosis as the primary method of cell death. An intercalative mode of interaction with DNA was determined, and pronounced double-strand cleavage of supercoiled DNA was observed.

    2. Indium Oxide Nanomaterials

      Controlled Synthesis of Monodispersed Sub-50 nm Nanoporous In2O3 Spheres and Their Photoelectrochemical Performance

      Qi Liu, Wen Zhang, Rongmei Liu and Guobing Mao

      Article first published online: 15 JAN 2015 | DOI: 10.1002/ejic.201402878

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      Uniform nanoporous In2O3 nanospheres about 50 nm in diameter with high surface areas were synthesized through a simple one-step solvothermal route with ethylenediamine as the solvent. Their photoelectrochemical properties were evaluated after treatment at different calcination temperatures.

    3. Luminescent Rhenium(I) Complexes

      Rhenium(I) Complexes with Alkynylphosphane Ligands: Structural, Photophysical, and Theoretical Studies

      Ilya Kondrasenko, Kristina S. Kisel, Antti J. Karttunen, Janne Jänis, Elena V. Grachova, Sergey P. Tunik and Igor O. Koshevoy

      Article first published online: 14 JAN 2015 | DOI: 10.1002/ejic.201403053

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      A family of mono- and bidentate alkynylphosphane-rhenium(I) phenanthroline complexes display intense photoluminescence at room temperature both in solution and in the solid state, with the quantum yields reaching 44 %. Modulation of the luminescence characteristics in the solid state has been achieved through variation of the rigidity of the environment.

    4. Photoluminescence

      Photoluminescent One-Dimensional Coordination Polymers from Suitable Pyridine Antenna and LnCl3 for Visible and Near-IR Emission

      Philipp R. Matthes, Jennifer Eyley, Johannes H. Klein, Ana Kuzmanoski, Christoph Lambert, Claus Feldmann and Klaus Müller-Buschbaum

      Article first published online: 14 JAN 2015 | DOI: 10.1002/ejic.201402973

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      The one-dimensional coordination polymers 1[LnCl3(bipy)(py)2]·py [bipy = 4,4′-bipyridine, py = pyridine; Ln = Gd, Tb, Dy, Ho, Er, Yb] exhibit photoluminescence properties in the visible and infrared region with a tunable energy gap between excitation and emission from UV to near-IR (NIR). The pyridyl ligands act as sensitizers, and the Ln3+-centred emission has quantum yields of up to 86 %.

    5. Metallacycles

      Pyrididine–Carboxylate Ligands as Double-Bridge Spacers in CuI Metallacycles

      Xialu Wu, Wenhua Zhang, Xinhai Zhang, Nini Ding and T. S. Andy Hor

      Article first published online: 14 JAN 2015 | DOI: 10.1002/ejic.201402930

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      Pyridine–carboxylate-bridged dinuclear CuI complexes capped by 1,1′-bis(diphenylphosphanyl)ferrocene (dppf) exhibit macrocycles with diagonal distances of 6.586, 9.159, and 10.006 Å. Such cavity sizes are formed by the introduction of CH=CH or phenyl units into the original pyridine-3-carboxylic acid (3-PyCOOH) spacer.

    6. Bio-Inspired Diiron Complexes

      Synthesis and Characterization of Bio-Inspired Diiron Complexes and Their Catalytic Activity for Direct Hydroxylation of Aromatic Compounds

      Xiao Wang, Tianyong Zhang, Qiusheng Yang, Shuang Jiang and Bin Li

      Article first published online: 14 JAN 2015 | DOI: 10.1002/ejic.201402918

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      Three FeI–FeI organometallic complexes were synthesized and used as highly selective catalysts for the direct hydroxylation of aromatic compounds to phenols, forming FeII–μ-O–FeII intermediates as the active oxygen-transfer species.

    7. Polypyridyl Complexes

      Homoleptic and Heteroleptic Ruthenium(II) Complexes Based on 2,6-Bis(quinolin-2-yl)pyridine Ligands – Multiple-Charged-State Modules for Potential Density Memory Storage

      Ion Marin, Constantin Turta, Andrew C. Benniston, Ross W. Harrington and William Clegg

      Article first published online: 12 JAN 2015 | DOI: 10.1002/ejic.201403088

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      The ligands diethyl 2,2′-(pyridine-2,6-diyl)bis(quinolone-4-carboxylate) (L2) and 2,6-bis(4-methylquinolin-2-yl)pyridine (L1) were used to prepare the homoleptic [Ru(L1)2][PF6]2 (RU1) and heteroleptic [Ru(L1)(L2)][PF6]2 (RU2) complexes. Electrochemistry experiments showed that the complexes can hold up to five electrons reversibly.

    8. Hydrogen Generation

      The Nature of Hydrogen Production from Aqueous-Phase Methanol Dehydrogenation with Ruthenium Pincer Complexes Under Mild Conditions

      Ming Lei, Yuhui Pan and Xuelu Ma

      Article first published online: 12 JAN 2015 | DOI: 10.1002/ejic.201403027

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      A density functional theory (DFT) study unveils the nature of the aqueous-phase methanol dehydrogenation to dihydrogen and carbon dioxide catalyzed by a ruthenium pincer complex. Three catalytic cycles of methanol, formaldehyde, and formate dehydrogenations were investigated.

    9. Silylphosphanides of Al, Ga, In

      Synthesis, Structures and Thermal Decomposition of Monomeric Aluminium, Gallium and Indium Silylphosphanides

      Manuel Kapitein and Carsten von Hänisch

      Article first published online: 12 JAN 2015 | DOI: 10.1002/ejic.201402996

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      A series of new N-heterocyclic carbene (NHC)-stabilized monomeric metal silylphosphanides of aluminium, gallium and indium were characterized through single-crystal X-ray diffraction and their structural and thermal properties are described.

    10. Interpenetrating Frameworks

      A Fivefold Interpenetrating dmd Topological Copper(I) Cyanide Complex Formed by C–C Bond Cleavage of Acetonitrile

      Lin Li, Chun-Hai Wang, Xia-Li Zhang and Xi Liu

      Article first published online: 12 JAN 2015 | DOI: 10.1002/ejic.201403037

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      The copper(I) cyanide complex Cu3(CN)3(4,4′-Hbpt)2 [4,4′-Hbpt = 3,5-bis(4-pyridyl)-1H-1,2,4-triazole] with a fivefold interpenetrating dmd topological framework was synthesized by C–C cleavage of acetonitrile under solvothermal conditions and emits violet luminescence.

    11. Li14(PON3)2O – A Non-Condensed Oxonitridophosphate Oxide

      Dominik Baumann and Wolfgang Schnick

      Article first published online: 9 JAN 2015 | DOI: 10.1002/ejic.201403125

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      Li14(PON3)2O, the first ortho-oxonitridophosphate, was synthesized by using a high-temperature deprotonation synthesis and its structure was determined based on X-ray powder diffraction data. It crystallizes in a trigonal structure that can be understood as a defect variant of the cubic antifluorite structure type.

    12. N-Heterocyclic Carbene Complexes

      Bifunctional N-Heterocyclic Carbene Ferrocenyl Ligands – Synthesis and Palladium(II) Complexes

      Pauline Loxq, Jean-Claude Daran, Eric Manoury, Rinaldo Poli and Agnès Labande

      Article first published online: 9 JAN 2015 | DOI: 10.1002/ejic.201403001

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      Two ferrocenylimidazolium tetrafluoroborate salts, precursors of new ferrocenylimidazol-2-ylidene bifunctional ligands, and the corresponding palladium(II) complexes have been prepared for the first time.

    13. Doped ZnS Nanostructures

      An Effective Two-Emulsion Approach to the Synthesis of Doped ZnS Crystalline Nanostructures

      Paolo Dolcet, Chiara Maurizio, Maurizio Casarin, Luciano Pandolfo, Stefano Gialanella, Denis Badocco, Paolo Pastore, Adolfo Speghini and Silvia Gross

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejic.201403004

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      We report the use of miniemulsions for the controlled synthesis of M-doped (M = CuII, MnII, SmIII, GdIII, or TbII) ZnS nanostructures (with crystallite size of 5–10 nm). The adopted synthetic route is ideally suited to easily achieve small particle sizes and narrow size distribution. The incorporation of the doping ions in the matrix is discussed.

    14. Hydroxyapatites

      Preparation, Characterization, and Thermal Transformation of Poorly Crystalline Sodium- and Carbonate-Substituted Calcium Phosphate

      Nataliia Strutynska, Igor Zatovsky, Nikolai Slobodyanik, Anna Malyshenko, Yuriy Prylutskyy, Oleg Prymak, Igor Vorona, Stanislav Ishchenko, Nikolai Baran, Alexander Byeda and Alexander Mischanchuk

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejic.201402761

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      Nanoparticles of complex substituted calcium phosphates are obtained by two wet synthesis techniques. The heating of samples to 700 °C causes the formation of Na+- and CO32–-containing apatite. The thermal stability to aggregation at 550–600 °C of the nanoparticles depends on their chemical composition.

    15. Functional Models of Enzymes

      Oxalate Oxidase Model Studies – Substrate Reactivity

      Piotr L. Pawlak, Manashi Panda, Jia Li, Atanu Banerjee, Derek J. Averill, Borislava Nikolovski, Brian J. Shay, William W. Brennessel and Ferman A. Chavez

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejic.201402835

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      MnLCl (HL = 1-benzyl-4-acetato-1,4,7-triazacyclononane) is investigated as a structural and functional model for oxalate oxidase. MnLCl effects the catalytic degradation of oxalate ions under ambient conditions. MnLCl is converted to a light-sensitive intermediate during catalysis. Analysis of the reaction mixture indicates that 1 equiv. of CO2 per oxalate ion is produced along with a HCO3 ion.

    16. Hybrid Conjugated Polymers

      Luminescent Polythiophene-Based Main-Chain Polyoxometalate-Containing Conjugated Polymers with Improved Solar-Cell Performance

      Ruixin Wang, Yong Li, Kuldeep Shetye, Tanmoy Dutta, Lu Jin, Shaohua Li and Zhonghua Peng

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejic.201402839

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      The first polythiophene-based main-chain polyoxometalate-containing conjugated polymer, synthesized by using the Stille polycondensation reaction, exhibits good photovoltaic properties.

    17. Speciation

      pH-Specific Halide-Dependent Materials from ZrIV/Hydroxycarboxylic Acid/Aromatic Chelator Reactivity: Architecture–Lattice Dimensionality and Spectroscopic Fingerprint Relations

      Eleftherios Halevas, Asimenia Karamelidou, Antonios Hatzidimitriou, Constantin Mateescu and Athanasios Salifoglou

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejic.201402864

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      The pH-specific reactivity of binary/ternary ZrIV/citric (malic) acid/(phenanthroline) systems leads to inorganic/organic hybrid Zr2O2-containing dinuclear assemblies with distinct 3D architectures. Structural speciation reveals the influence of halide on the ultimate structure and well-defined factor correlations earmarking spectroscopic identity in the design of advanced materials.

    18. Bimetallic Complexes

      Structures and Magnetic Properties of Bis(μ-phenoxido), Bis(μ-phenoxido)-μ-carboxylato and Bis(μ-phenoxido)bis(μ-carboxylato) FeIIINiII Compounds – Magnetostructural Correlations

      Sujit Sasmal, Shuvayan Roy, Luca Carrella, Arpita Jana, Eva Rentschler and Sasankasekhar Mohanta

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejic.201402866

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      The syntheses, characterization, crystal structures and magnetic properties of the FeIIINiII compounds [FeIII(N3)2L1NiII(H2O)2](ClO4) (1), [FeIII(benzoato)L1NiII(H2O)(μ1,3-benzoato)](ClO4) (2), [FeIII(benzoato)L2NiII(H2O)(μ1,3-benzoato)](ClO4) (3), [FeIIIL2NiII1,3-acetato)2](ClO4)·H2O (4) and [FeIIIL2NiII1,3-propionato)2](ClO4)·H2O (5; L1, L2 = tetraiminodiphenol macrocycles) are described.

    19. Red-Emitting Nanophosphors

      Luminescence Enhancement of Lu3TaO7:Eu3+@Lu3TaO7 Red-Emitting Nanophosphors

      Yuan Zhang, Wenchun Feng, Keke Huang, Long Yuan, Yanyan Du, Xiaofeng Wu and Shouhua Feng

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejic.201402874

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      A series of red-emitting homogeneous Lu3TaO7:Eu3+@Lu3TaO7 (core-shell) nanoparticles have been successfully synthesised by means of a two-step simple hydrothermal process. The emission intensity was improved by 31.5 % compared with the bare cores and the quantum yield increased by 142 %.

    20. Molybdenum Alkoxides

      Developing Pathways to the Synthesis of Low-Valence Molybdenum Methoxides: Preparation, Characterization, and Redox Chemistry of Dimeric and Tetrameric Molybdenum Alkoxide Clusters

      Denis A. Kuznetsov, Ivan V. Fedyanin, Natal'ya S. Komarova, Gennady V. Shilov, Vyacheslav M. Martynenko, Sergey G. Vasil'ev, Alexander G. Krivenko, Konstantin A. Lyssenko and Tamara A. Bazhenova

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejic.201403032

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      A facile synthetic route to the Mo=Mo double-bonded dimer [Mo2Cl4(OCH3)4(CH3OH)2] (1) and its reactivity are described. The redox-active cluster [Mo4Cl4O2(OCH3)6(CH3OH)4] (4) featuring the unique {Mo4} core was obtained through two distinct pathways and characterized in the solid state and in solution by numerous techniques.

    21. Binding Modes of Complexes to DNA

      Tetraaza[14]macrocyclic Transition Metal Complexes as DNA Intercalators

      Iwona Mames, Alison Rodger and Jarosław Kowalski

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejic.201403042

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      This paper describes the synthesis of simple cyclidene-based DNA intercalators. Their ability to bind to DNA was studied using various methods including linear and circular dichroism. The determined binding constants are comparable to those calculated for analogous anthracene and pyrene derivatives.

    22. Core-Shell Nanoparticles

      Surface-Selective Deposition of a Reusable Gold Catalyst on a Thin Film of Metal Hydroxide Nanocrystals

      Hye Ran Cho and Jong Hyeon Lee

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejic.201403054

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      Uniform gold nanoparticles (Au NPs) are preferentially deposited on the surface of layered double hydroxide (LDH) nanocrystals that densely cover a glass substrate. The LDH surfaces play an important role in the growth of the Au NPs and in stabilizing them against agglomeration. This hybrid film exhibits superior catalytic efficiency and reusability for the reduction of p-nitrophenol with NaBH4.

  13. Microreviews

    1. Ionogels

      Electrospinning of Ionogels: Current Status and Future Perspectives

      Andreas Taubert

      Article first published online: 25 NOV 2014 | DOI: 10.1002/ejic.201402490

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      Spin it: Electrospinning is a useful and low-cost approach towards high-surface-area nanofibrous ionogels, that is, multifunctional hybrid materials based on ionic liquids, with tremendous application potential from catalysis to energy, healthcare, and beyond. The article provides an overview of the field and discusses the future potential of these promising materials.

  14. Full Papers

    1. Two-Photon Absorption

      Two-Photon Absorption Properties of Eu3+-DPA-Triazolyl Complexes and the Derived Silica Nanoparticles Embedding These Complexes

      Pierre Adumeau, Claire Gaillard, Damien Boyer, Jean-Louis Canet, Arnaud Gautier and Rachid Mahiou

      Article first published online: 21 NOV 2014 | DOI: 10.1002/ejic.201402617

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      The TRS technique is used at 300 K to analyze the phosphorescence and the NIR excitation spectra of Gd3+-, Eu3+-DPA-triazolyl complexes and derived NPs embedding them. The TPA excitation spectra of the NPs are located on the low-energy side of the phosphorescence spectrum and consist of narrow bands attributed to the S0(0)[RIGHTWARDS ARROW]T1(0–2) pure electronic transition.

    2. Imaging Agents

      Glycine–Nitrate Process for the Elaboration of Eu3+-Doped Gd2O3 Bimodal Nanoparticles for Biomedical Applications

      Graziella Goglio, Gaganpreet Kaur, Sonia L. C. Pinho, Nicolas Penin, Alexia Blandino, Carlos F. G. C. Geraldes, Alain Garcia and Marie-Helene Delville

      Article first published online: 18 NOV 2014 | DOI: 10.1002/ejic.201402721

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      By fine control of the flame temperature in the glycine–nitrate process, highly crystalline Eu3+-doped and undoped Gd2O3 nanoparticles are obtained. In the doped samples, the Eu3+ ions are homogeneously distributed over the whole material. The Eu:Gd2O3 NPs are highly luminescent and exhibit relaxivities that define them as potential T1 contrast agents for biomedical applications.

    3. Crystal Nucleation

      Molecular Mechanisms of [Bi6O4(OH)4](NO3)6 Precursor Activation, Agglomeration, and Ripening towards Bismuth Oxide Nuclei

      Markus Walther and Dirk Zahn

      Article first published online: 13 NOV 2014 | DOI: 10.1002/ejic.201402751

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      Molecular dynamics simulations unravel the early steps of bismuth oxide precursor association and ripening into larger aggregates. Nitrate ions play a twofold role in the process by preventing the association of Bi6O4(OH)4(NO3)6 clusters but at the same time inducing the formation of oligomers comprising under-coordinated Bi ions.

  15. Microreviews

    1. Host–Guest Chemistry

      Possible Roles of the Spatial Distribution of Organic Guest Species in Mesoporous Silicas to Control the Properties of the Hybrids

      Makoto Ogawa, Kanji Saito and Minoru Sohmiya

      Article first published online: 12 NOV 2014 | DOI: 10.1002/ejic.201402651

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      The spatial distribution (location, density, and orientation) of the functional units (guest species) attached/included on/in mesoporous silicas are discussed to highlight the status of the host–guest chemistry of mesoporous silicas.

  16. Full Papers

    1. Polyurethane Nanocomposites

      Synthesis of Advanced Nanoreinforced Polyurethane with Thiolene Photografted Organo-Modified Layered Double Hydroxide

      Audrey Ramoné, Audrey Diouf-Lewis, Florence Delor-Jestin, Rémi Auvergne, Sylvain Caillol, Vincent Verney and Fabrice Leroux

      Article first published online: 12 NOV 2014 | DOI: 10.1002/ejic.201402602

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      Successive processes to yield layered double hydroxide filled polyurethane nanocomposite including (1) organo-modification of LDH platelets, (2) functionalization using UV thiolene coupling and (3) monomer addition.

    2. Electrolytes

      Hybrid Polymer Electrolytes Based on a Poly(vinyl alcohol)/Poly(acrylic acid) Blend and a Pyrrolidinium-Based Ionic Liquid for Lithium-Ion Batteries

      Savitha Thayumanasundaram, Vijay Shankar Rangasamy, Niels De Greef, Jin Won Seo and Jean-Pierre Locquet

      Article first published online: 11 NOV 2014 | DOI: 10.1002/ejic.201402603

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      Mechanically stable polymer membranes for lithium-ion batteries consist of 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (PYR14TFSI) doped with 0.2 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).

    3. Water Splitting

      Synthetic Strategies for Variably Substituted Ruthenium–Imidazophenanthrolinium Complexes

      Lydia Petermann, Robert Staehle, T. David Pilz, Dieter Sorsche, Helmar Görls and Sven Rau

      Article first published online: 28 OCT 2014 | DOI: 10.1002/ejic.201402669

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      Different synthetic strategies are investigated for the synthesis of variably substituted ruthenium–imidazophenanthrolinium complexes. Structural and preliminary photochemical characterizations suggest that substitution patterns can be altered without influencing the photochemical properties.

  17. Microreviews

    1. Carbon Materials

      Ionic Liquid Based Approaches to Carbon Materials Synthesis

      Zai-Lai Xie and Dang Sheng Su

      Article first published online: 14 OCT 2014 | DOI: 10.1002/ejic.201402607

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      Ionic liquids are currently established solvents, precursors for carbon materials, and components of carbon-based ionogels. The unique properties of ionic liquids are beneficial for the formation of unusual carbon materials or composites with homogeneous heteroatom doping (e.g., N, B, S) and controllable porosity.

  18. Full Papers

    1. Nanocomposite Films

      Preparation of Alginate/Graphene Oxide Hybrid Films and Their Integration in Triboelectric Generators

      Luca Valentini, Nicoletta Rescignano, Debora Puglia, Marta Cardinali and Josè Kenny

      Article first published online: 6 OCT 2014 | DOI: 10.1002/ejic.201402610

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      Sodium alginate/graphene oxide nanocomposite films were prepared by a solvent-casting method. We report the proof of concept that such a hybrid system can be used as the active component of a triboelectric generator. The involvement of a biodegradable polymer might introduce new applications in biodegradable/biocompatible electronics.

    2. Layered Compounds

      Nanostructuring of Bridged Organosilane Precursors with Pendant Alkyl Chains

      Sílvia C. Nunes, Kristýna Bürglová, Jana Hodačová, Rute A. S. Ferreira, Luís D. Carlos, Paulo Almeida, Xavier Cattoën, Michel Wong Chi Man and Verónica de Zea Bermudez

      Article first published online: 1 OCT 2014 | DOI: 10.1002/ejic.201402673

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      A new bridged silsesquioxane with hierarchically structured lamellar bilayer structure and a texture composed of microplates of nanometer thickness was obtained by sol-gel and self-assembly by using a bridged organosilane carrying a pendant icosanyl chain produced by click chemistry. The hybrid exhibits a time-independent reversible order/disorder phase transition in a heating-cooling cycle.

  19. Microreviews

    1. Supramolecular Chemistry

      Constitutional Hybrid Materials – Toward Selection of Functions

      Mihail Barboiu

      Article first published online: 29 SEP 2014 | DOI: 10.1002/ejic.201402500

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      This review will focus on the implementation of constitutional dynamic chemistry (CDC) toward constitutional hybrid materials, emphasizing recent developments in biomimetic ion channels, membranes, and constitutional hybrid materials.

  20. Full Papers

    1. Conformation Studies

      Conformational Changes and Phase Behaviour in the Protic Ionic Liquid 1-Ethylimidazolium Bis(trifluoromethylsulfonyl)imide in the Bulk and Nano-Confined State

      Anna Martinelli

      Article first published online: 29 SEP 2014 | DOI: 10.1002/ejic.201402496

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      Conformational changes of the TFSI anion in the protic ionic liquid C2HImTFSI have been monitored by temperature-dependent Raman spectroscopy for the bulk and nano-confined states. Phase behaviours have also been spectroscopically investigated at a range of temperatures. In the nano-confined state the cis form predominates and the enthalpic term was higher.

    2. Ionic Liquids

      Organic–Inorganic Hybrid Membranes Based on Sulfonated Poly(ether ether ketone) and Tetrabutylphosphonium Bromide Ionic Liquid for PEM Fuel Cell Applications

      Vijay Shankar Rangasamy, Savitha Thayumanasundaram, Niels de Greef, Jin Won Seo and Jean-Pierre Locquet

      Article first published online: 19 SEP 2014 | DOI: 10.1002/ejic.201402558

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      Polymer–ionic liquid electrolyte membranes were fabricated from tetrabutylphosphonium bromide ([P4 4 4 4]Br) and sulfonated poly(ether ether ketone) (SPEEK). Their thermal, mechanical, structural and electrical properties show promise for their use in high-temperature fuel cell applications.

    3. Polymorphs

      Prospective Electroluminescent Hybrid Materials

      Olga B. Petrova, Roman I. Avetisov, Andew V. Khomyakov, Rasim R. Saifutyarov, Alina A. Akkuzina, Elena N. Mozhevitina, Alexandr V. Zhukov and Igor Ch. Avetissov

      Article first published online: 12 SEP 2014 | DOI: 10.1002/ejic.201402538

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      Three polymorphs of tris(8-hydroxyquinoline)boron (Bq3) were obtained by high-temperature substitution reaction. Their spectral and structural properties were investigated and showed Bq3 to be a potential blue emitter. Hybrid material (HM) films B2O3/Alq3/B2O3 on a glass substrate were made by vacuum sputtering. Laser heating of the HM film resulted in an irreversible change in its photoluminescence.

    4. Surface Functionalization

      Spatially Confined Functionalization of Transparent NiO Thin Films with a Luminescent (1,10-Phenanthroline)tris(2-thenoyltrifluoroacetonato)europium Monolayer

      Emanuele Smecca, Cristina Tudisco, Antonino E. Giuffrida, Maria R. Catalano, Adolfo Speghini, Graziella Malandrino and Guglielmo G. Condorelli

      Article first published online: 12 SEP 2014 | DOI: 10.1002/ejic.201402479

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      Anchoring of the Eu(TTA)3phen complex on MOCVD-grown NiO films is reported. The NiO surface was activated by means of a sputtering process and functionalized with a phosphonic linker, followed by the coordination of the Eu complex through a ligand-exchange reaction. The luminescent hybrid system has been proven to retain the optical properties of the Eu complex.

    5. Self-Healing Materials

      Furan-Modified Spherosilicates as Building Blocks for Self-Healing Materials

      Tom Engel and Guido Kickelbick

      Article first published online: 9 SEP 2014 | DOI: 10.1002/ejic.201402551

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      Octameric furfuryl-functionalized spherosilicates were used to prepare self-healing hybrid materials based on a reversible Diels–Alder reaction. Two different bismaleimides were used as dienophilic cross-linkers for the self-healing materials. The healing abilities are dictated by the nature of the cross-linker.

    6. Coordination Polymers

      Coordination Polymers Based on Alkylboronate Ligands: Synthesis, Characterization, and Computational Modelling

      Dorothée Berthomieu, Christel Gervais, Guillaume Renaudin, Marc Reinholdt, Saad Sene, Mark E. Smith, Christian Bonhomme and Danielle Laurencin

      Article first published online: 9 SEP 2014 | DOI: 10.1002/ejic.201402561

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      The synthesis and characterization of three new crystalline alkylboronate structures are described, together with their DFT modelling and calculations of solid-state NMR parameters and IR O–H stretching frequencies.

    7. Luminescence

      Modelling the Luminescence of Phosphonate Lanthanide–Organic Frameworks

      Mariela M. Nolasco, Ricardo F. Mendes, Patrícia P. Lima, Filipe A. Almeida Paz, Luís D. Carlos and João Rocha

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402492

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      The applicability of the LUMPAC software for calculations of the photoluminescence properties of metal–organic frameworks is assessed by considering three systems with a ditopic 1,4-phenylenebis(methylene)diphosphonic acid ligand and Eu3+ ions. A simple method based on the crystallographic structural subunits affords excellent agreement between the calculated and experimental photoluminescence.

    8. Gas Adsorbing Materials

      Efficient Hybrid-Type CO2 Adsorbents of Reassembled Layered Double Hydroxide 2D Nanosheets with Polyoxometalate 0D Nanoclusters

      Jayavant L. Gunjakar, In Young Kim and Seong-Ju Hwang

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejic.201402480

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      Porous nanohybrids of Mg-Al-layered double hydroxide (LDH) 2D nanosheets and polyoxometalate 0D nanoclusters are synthesized by an exfoliation–reassembling process. The resulting nanohybrid materials show promising CO2 adsorption capabilities exceeding those of pristine Mg-Al-LDH, underscoring the usefulness of the present hybridization method in optimizing gas adsorption by LDH materials.

    9. Biosensing

      Properties of an Indium Tin Oxide Electrode Modified by a Laser Nanostructured Thin Au Film for Biosensing

      Katarzyna Grochowska, Katarzyna Siuzdak and Gerard Śliwiński

      Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402485

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      Thin Au films on ITO that were stepwise patterned by means of nanosecond UV laser pulses transformed into semi-regular nanoparticle arrays. The modified electrode showed enhanced activity towards ferricyanide redox systems as well as glucose, and can be considered for the production of a non-enzymatic biosensor.

    10. Composite Structures

      Optical and Electrooptical Properties of Porous-Silicon/Conjugated-Polymer Composite Structures

      Amit Nahor, Itai Shalev, Amir Sa'ar and Shlomo Yitzchaik

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402450

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      An organic–inorganic hybrid structure consisting of porous silicon and nanowires of poly(N-vinylcarbazole) (PVK) exhibits optical behavior of the PVK nanowires, which is unique when compared with the bulk material. Furthermore, a simple method to control the band alignment between type-I and type-II is demonstrated. Our results enable a variety of applications and electrooptical characteristics.

    11. Selective Crystallization

      Sulfonated Polymethylsiloxane as an Additive for Selective Calcium Oxalate Crystallization

      Andrónico Neira-Carrillo, Fabian Luengo-Ponce, Patricio Vásquez-Quitral, Mehrdad Yazdani-Pedram, María Soledad Fernández, Helmut Cölfen and José Luis Arias

      Article first published online: 27 JUN 2014 | DOI: 10.1002/ejic.201402063

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      Sulfonated and fluorescent polymethylsiloxanes (SO3H-PMS) were synthesized and used as additives for in vitro calcium oxalate (CaOx) crystallization. The strong modifying capacity of SO3HPMS on CaOx morphologies and CaOx monohydrate (COM) and CaOx dihydrate (COD) crystal types was demonstrated. Fluorescent CaOx crystals were also produced by the inclusion of SO3H-PMS into the CaOx matrix.

    12. Nickel Nanoparticles

      A Neutral 1D Coordination Polymer Constructed from the NiII Complex of the N-Phosphorylated Thiourea PhNHC(S)­NHP­(O)(OPh)2 and Pyrazine: A Single-Source Precursor for Nickel Nanoparticles

      Maria G. Babashkina, Damir A. Safin, Koen Robeyns and Yann Garcia

      Article first published online: 3 JUN 2014 | DOI: 10.1002/ejic.201402278

      Thumbnail image of graphical abstract

      Interaction of [Ni{PhNHC(S)NP(O)(OPh)2}2] with pyrazine (pz) yielded the 1:1 coordination polymer [NiL2pz]n, in which the coordination mode of L changed unexpectedly from 1,3-N,S- to 1,5-O,S-[NiL2pz]n dissolved in tri-n-octylphosphine (TOP) is decomposed in hot hexadecylamine to give TOP-capped face-centered cubic Ni nanoparticles with an average particle size of 17(2) nm.

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