European Journal of Inorganic Chemistry

Cover image for Vol. 2016 Issue 17

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

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.942

ISI Journal Citation Reports © Ranking: 2014: 9/45 (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 - 100
  2. 101 - 102
  1. Full Papers

    1. Phosphorus Heterocycles

      One-Pot Synthesis of Phosphanylbis(N-arylglycines) and Spontaneous Diastereoselective Lactamization of P-Alkyl Derivatives To Form Five-Membered P,N-Heterocyclic Amino Acids

      Joanna Lach, Gottfried J. Palm, Peter G. Jones and Joachim W. Heinicke

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/ejic.201600202

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      PhPH2 reacts with glyoxylic acid hydrate and a primary aniline (1:2:2) in Et2O to afford a rac/meso-mixture of corresponding phosphanyl-bis(glycine) 1. Under the same mild conditions, more P-basic primary alkylphosphanes CyPH2 and iBuPH2, undergo diastereoselective lactamization affording phosphaproline derivatives 2 and 3; the structure of 2 was amenable to X-ray crystallography.

    2. Synthesis of Mononuclear Complexes

      Making Use of Obstacles: Alternative Synthetic Approaches towards Osmium(II)-Based Photochemical Molecular Devices

      Johannes Habermehl, Dieter Sorsche, Petra Murszat and Sven Rau

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/ejic.201600239

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      Two synthetic pathways lead to a red-light-absorbing mononuclear osmium complex incorporating a potential bridging ligand. In situ reduction of an OsIII precursor leads to facile access to the target compound owing to virtual dilution.

    3. Bimetallic Frameworks

      Rational Design of Two-Dimensional Bimetallic Wave Structures from Zigzag Chains via Site-Specific Coordination around the 2,6-Naphthalenediphosphonic Acid Motif

      Aysun Bulut, Yunus Zorlu, Michael Wörle, Salih Paşa, Hüseyin Kurt, Jon Zubieta, Jens Beckmann and Gündoğ Yücesan

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/ejic.201600309

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      The preparation of one-, two-, and three-dimensional metal–organophosphonate frameworks from a V-shaped molecular precursor is reported.

    4. C–C Coupling

      2,5-Norbornadiene C–C Coupling Reactions Mediated by Iridium Complexes

      M. Pilar Betoré, Miguel A. Casado, Pilar García-Orduña, Fernando J. Lahoz, Víctor Polo and Luis A. Oro

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/ejic.201600336

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      Five- and seven-membered iridacycles have been prepared by sequential C–C bond-forming reactions between 2,5-norbornadiene molecules.

    5. MOF Composites in Theranostics

      A Promising Catalytic and Theranostic Agent Obtained through the In-Situ Synthesis of Au Nanoparticles with a Reduced Polyoxometalate Incorporated within Mesoporous MIL-101

      Catherine Roch-Marchal, Tania Hidalgo, Hung Banh, Roland A. Fischer and Patricia Horcajada

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/ejic.201600359

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      Promising catalysts and optical contrast agents based on (Au)POM@MOF (POM = polyoxometalate, MOF = metal–organic framework) composites are synthesized in situ through the incorporation of a POM into the mesopores of MIL-101, followed by reduction to form Au nanoparticles. These composites are internalized rapidly by cells, and no Au/POM leaching or MOF biodegradation occurs.

    6. Fluorinated Phosphoranes

      Difluorotriorganylphosphoranes for the Synthesis of Fluorophosphonium and Bismuthonium Salts

      Sven Solyntjes, Beate Neumann, Hans-Georg Stammler, Nikolai Ignat'ev and Berthold Hoge

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/ejic.201600539

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      Highly reactive fluorophosphonium cations, [R3PF]+, previously unknown fluorobismuthonium cations, [R3BiF]+, and triarylbismuth dications, [R3Bi]2+, are conveniently available by the reactions of difluoro(triaryl)pnictogens with new difluoro(perfluoroorganyl)phosphoranes.

  2. Microreviews

    1. Hydrogen Isotope Separation

      Quantum Sieving for Separation of Hydrogen Isotopes Using MOFs

      Hyunchul Oh and Michael Hirscher

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600253

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      Two mechanisms for hydrogen isotope separation using MOFs are introduced: “kinetic quantum sieving (KQS) with confinement in small pores” and “chemical affinity quantum sieving (CAQS) by strong adsorption sites”. In addition, the recent status and future strategies for hydrogen isotope separation with the aid of MOFs is discussed.

  3. Full Papers

    1. Organotin Compounds

      23- and 27-Membered Macrocyclic Diorganotin(IV) Bis-dithiocarbamates: Synthesis, Spectroscopic Characterization, DFT Calculations, and Physicochemical Analysis as Anion Receptors

      María G. Vasquez-Ríos, Viviana Reyes-Márquez, Herbert Höpfl, Aaron Torres-Huerta, Jorge Guerrero-Álvarez, Mario Sánchez, Irán F. Hernández-Ahuactzi, Karen Ochoa-Lara, Arturo Jiménez-Sánchez and Rosa Santillán

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600254

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      Organotin-based macrocycles suitable for the selective recognition of fluoride and acetate have been structurally modified at three different sites to explore the effects of variations of the molecular configuration and conformation.

    2. MOFs for Sensors

      Vapochromic Luminescence of a Zirconium-Based Metal–Organic Framework for Sensing Applications

      Franziska Drache, Volodymyr Bon, Irena Senkovska, Marcus Adam, Alexander Eychmüller and Stefan Kaskel

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600261

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      Integration of fluorenone cores into a zirconium metal–organic framework (MOF) results in sensitive vapochromic luminescence. The MOF shows significant changes in the emission spectrum in response to solvent-vapour exposure, which makes this material a potential candidate for luminescence-based sensing applications.

    3. Vanadates

      Vanadium Polyoxoanions within Coordination Polymers Based on a Macrocyclic Nickel Complex: Structural Diversities and Single-Crystal to Single-Crystal Transformation

      Guang-Chuan Ou, Xian-You Yuan, Zhi-Zhang Li, Wen-Yi Li, Fei Zeng, Ji-Hua Deng and Di-Chang Zhong

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600284

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      Five coordination polymers have been constructed from a macrocyclic NiII complex and vanadium polyoxoanions. The vanadium polyoxoanions assume diverse structures, namely the [V16O42]n4n sheet, [V6O18]6– ring, [VO3]nn chain, [VO3]nn sheet, and [V10O29]n8n chain. Electrochemical measurements indicate that two of the coordination polymers are potential catalysts for water splitting.

    4. Metalloenzyme Electrode

      Anchoring Cytochrome b562 on a Gold Nanoparticle by a Heme–Heme Pocket Interaction

      Akira Onoda, Tomoaki Taniguchi, Nozomu Inoue, Ayumi Kamii and Takashi Hayashi

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600301

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      Gold nanoparticles were immobilized on a gold electrode surface. Apocytochrome b562 was then immobilized on the surface of the AuNP-modified electrode through a heme–heme pocket interaction. The hemoprotein-immobilized electrode exhibited a ten-fold enhanced electrochemical response relative to the protein immobilized directly on the gold electrode.

    5. Nickel Nanoparticle Catalysts

      Nickel Nanoparticles Supported on CMK-3 with Enhanced Catalytic Performance for Hydrogenation of Carbonyl Compounds

      Daeho Kim, Hyuntae Kang, Hyesu Park, Sungkyun Park, Ji Chan Park and Kang Hyun Park

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600318

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      Ni/CMK-3 was prepared by incorporating Ni particles formed inside the pores of CMK-3 by impregnation of nickel nitrate and subsequent hydrogen reduction. The prepared Ni/CMK-3 has a large surface area and a very small nickel nanoparticle size (1 nm) with the aim of achieving high performance in catalytic hydrogenation reactions.

    6. Phosphorus Biradicaloids

      Synthesis of a Silylated Phosphorus Biradicaloid and Its Utilization in the Activation of Small Molecules

      Alexander Hinz, René Kuzora, Anne-Kristin Rölke, Axel Schulz, Alexander Villinger and Ronald Wustrack

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600321

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      Silylated 1,3-dichloro-1,3-diphospha-2,4-diazane, [ClP(µ-NHyp)]2 [Hyp = Si(SiMe3)3], was reduced with activated magnesium to afford the silylated biradicaloid [P(µ-NHyp)]2, which was isolation and fully characterized. The activation of molecules bearing single and double bonds with [P(µ-NHyp)]2 was studied, yielding heteroatom cage compounds.

    7. Anticancer Complexes

      Iridium(III) Complexes of Terpyridine- and Terpyridine-Analogous Ligands Bearing Sugar Residues and Their in vitro Activity

      Aram Prokop, Justyna A. Czaplewska, Mara Clausen, Marcel König, Andreas Wild, Rico Thorwirth, Benjamin Schulze, Krzysztof Babiuch, David Pretzel, Ulrich S. Schubert and Michael Gottschaldt

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600325

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      A series of terpyridine and terpyridine-analogous ligands bearing sugar moieties attached by different glycosidic bonds and their IrIII complexes was synthesized and characterized. Studies on cell viability, selectivity, drug resistance in vitro, and the apoptosis mechanism were performed. The results revealed enhanced activity of a complex bearing acetylated thioglucose.

    8. Single-Molecule Magnets

      Tri- and Pentanuclear Complexes Derived from Manganese(III) Schiff Base and Hexacyanoferrate(III) Building Blocks

      Meng-Jiao Zhang, Yu-Ye Zhang, Chun Yang, Qing-Lun Wang and Dai-Zheng Liao

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600339

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      Two cyanido-bridged complexes are synthesized from the same [Mn(SB)(H2O)]+ (SB = Schiff base) and hexacyanoferrate(III) reactants. The first complex consists of cyanido-bridged linear trinuclear [{Mn(SB)}2{Fe(CN)6}] anions, which are further linked into 1D chains by biphenolate bridges. The second complex is a cyanido-bridged pentanuclear complex, which behaves as a single-molecule magnet.

    9. Metathesis Catalysts

      Remarkable Ability of the Benzylidene Ligand To Control Initiation of Hoveyda–Grubbs Metathesis Catalysts

      Tymoteusz Basak, Krzysztof Grudzień and Michał Barbasiewicz

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600435

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      Initiation of Hoveyda–Grubbs metathesis catalysts requires opening of the chelate ring, followed by ligand exchange in the initial turnover of the metathesis cycle. Our studies reveal that substitution at the 6-position of the benzylidene ring influences the latter process and shifts the complexes to the latent systems (Mes = 2,4,6-trimethylphenyl).

    10. Anion Radical Complexes

      Mixed-Valence o-Iminobenzoquinone and o-Iminobenzosemiquinonate Anion Radical Complexes of Cobalt: Valence Tautomerism

      Suvendu Maity, Suman Kundu, Sachinath Bera, Thomas Weyhermüller and Prasanta Ghosh

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600525

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      o-Iminobenzosemiquinonate anion radical (LSPhISQ·) and o-iminobenzoquinone (LSPhIQ) based mixed-valence complexes of cobalt of the types trans-[CoII(LSPhISQ0.5·)2X] {X = Cl, SCN(thiocyanato-kS), N3, NO2, and I3} (LSPhH2 = 2,4-di-tert-butyl-6-{[2-(phenylthio)phenyl]amino}phenol), which exhibit valence tautomerism in both solid and solution states are reported.

  4. Communications

    1. Heterometallic Complexes

      Efficient Synthesis of One- and Two-Dimensional Multimetallic Gold–Bis(dithiolene) Complexes

      Michihisa Murata, Shoji Kaji, Hidetaka Nishimura, Atsushi Wakamiya and Yasujiro Murata

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600595

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      We establish efficient and versatile methods for the synthesis of multimetallic gold–bis(dithiolene) complexes with well-defined structures. A two-dimensional trimetallic complex with a starburst structure is prepared and isolated in high yield. The solid-state structures of the complexes are unambiguously revealed by X-ray diffraction analyses.

  5. Full Papers

    1. Polyoxometalates

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      Photophysical Characterization and Recognition Behaviour of a Bis(dansylated) Polyoxometalate

      Mauro Carraro, Giacomo Bergamini, Michele Di Lauro, Gloria Modugno, Massimo Baroncini, Paola Ceroni and Marcella Bonchio

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600636

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      A bis(dansylated) polyoxotungstate has been characterized to highlight the photophysical interplay between its two functional domains: a tweezer-like motif, defined by the dansyl units, and the polyanionic inorganic scaffold. The two subunits shape a ditopic receptor, being able to interact with lanthanide ions and with cationic organic chromophores, which trigger different spectral and morphological responses

    2. Anion Radical Complexes

      o-Iminobenzoquinone and o-Iminobenzosemiquinonate Anion Radical Complexes of Rhodium and Ruthenium

      Suvendu Maity, Suman Kundu, Sachinath Bera, Thomas Weyhermüller and Prasanta Ghosh

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600526

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      o-Iminobenzosemiquinonate anion radical (LSPhISQ·) and o-iminobenzoquinone (LSPhIQ) complexes of rhodium and ruthenium of types cis-[RhIII(LSPhISQ·)(PPh3)Cl2] (1) and cis-[RuII(LSPhIQ)(PPh3)Cl2] (2) (LSPhH2 = 2,4-di-tert-butyl-6-{[2-(phenylthio)phenyl]amino}phenol) are reported. The existence of valence tautomeric equilibrium of type [RhIII(LSPhISQ·)] ⇌ [RhII(LSPhIQ)] in 1 was established.

    3. Gas Separation

      Flexible Metal–Organic Frameworks with Discriminatory Gate-Opening Effect for the Separation of Acetylene from Ethylene/Acetylene Mixtures

      Libo Li, Rajamani Krishna, Yong Wang, Xiaoqing Wang, Jiangfeng Yang and Jinping Li

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600182

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      Two flexible metal–organic frameworks (MOFs) exhibit gate-opening-type adsorption properties for acetylene but not for ethylene, leading to a highly selective adsorption of acetylene over ethylene at 273–298 K. The results suggest the potential of both flexible MOFs for industrial acetylene/ethylene separation through the energy-efficient adsorption separation process.

    4. Electrostatic Properties of NHCs

      Electrostatic Properties of N-Heterocyclic Carbenes Obtained by Experimental Charge-Density Analysis of Two Selenium Adducts

      Hannes Buhl, Kathrin Verlinden, Christian Ganter, Sladjana B. Novaković and Goran A. Bogdanović

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/ejic.201600292

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      High-resolution X-ray diffraction experiments (100 K) have been used to investigate and quantitatively compare the electron density distribution in two carbene adducts of selenium.

    5. Supported Catalysts

      Highly Stable and Active Palladium Nanoparticles Supported on a Mesoporous UiO66@reduced Graphene Oxide Complex for Practical Catalytic Applications

      Xiang Liu, Xiaohua Zhao, Ming Zhou, Yuanyuan Cao, Haiyan Wu and Jianjun Zhu

      Version of Record online: 21 JUN 2016 | DOI: 10.1002/ejic.201600367

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      A novel UiO66@RGO-Pd composite was designed and used as an outstanding catalyst for the reduction of nitroarenes with NaBH4 as the reducing agent in EtOH. The hybrid-material catalyst could be recycled and reused after simple filtration, while keeping similar catalytic activity for six successive reactions.

    6. MOF Sensors

      Microporous Metal–Organic Frameworks Based on Zinc Clusters and Their Fluorescence Enhancements towards Acetone and Chloroform

      Kangcai Wang, Zhien Lin, Shi Huang, Jie Sun and Qinghua Zhang

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/ejic.201600184

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      Two fluorescent metal–organic frameworks constructed with d10-configured metal clusters (i.e., Zn3 and Zn7O2) and organic carboxylic acid ligands (i.e., 1,4-dicarboxybenzene and 1,4-naphthalenedicarboxylic acid) are synthesized. They show interesting fluorescence enhancement effects towards acetone and chloroform, respectively.

    7. Silicon

      SO2 Activation by the Bis(guanidinato)silylene [iPrNC(NiPr2)NiPr]2Si: Formation of Neutral Six-Coordinate Silicon(IV) Complexes with a Chelating Sulfito or Dithionito Ligand

      Felix M. Mück, Johannes A. Baus, Rüdiger Bertermann and Reinhold Tacke

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/ejic.201600294

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      Activation of SO2 by the donor-stabilized bis(guanidinato)silylene 1 leads to the six-coordinate sulfitosilicon(IV) complex 2 or dithionitosilicon(IV) complex 3 (co-crystallizate of cis-3 and trans-3). Compounds 2 and 3 represent very rare examples of main-group element compounds with an O,O-chelating sulfito or dithionito ligand.

    8. Nanoborides

      A Size-Dependent Analysis of the Structural, Surface, Colloidal, and Thermal Properties of Ti1–xB2 (x = 0.03–0.08) Nanoparticles

      Bürgehan Terlan, Aleksandr A. Levin, Felix Börrnert, Julian Zeisner, Vladislav Kataev, Marcus Schmidt and Alexander Eychmüller

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/ejic.201600315

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      We report the size-dependent structural, surface, colloidal, and thermal properties of the well-known refractory material titanium diboride prepared at the nanoscale by a size-controlled inorganic molten-salt technique.

    9. Separation of Lanthanides

      A Computational Approach to Predicting Ligand Selectivity for the Size-Based Separation of Trivalent Lanthanides

      Alexander S. Ivanov and Vyacheslav S. Bryantsev

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/ejic.201600319

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      We report an approach based on quantum chemical calculations that achieves high accuracy in predicting aqueous-phase selectivity across the lanthanide series. Quantitative agreement with experiment demonstrates the potential of the method for accelerated computer-aided discovery of superior ligands for selective lanthanide ion complexation.

  6. Communications

    1. Proton-Conducting MOFs

      10000-Fold Enhancement in Proton Conduction by Doping of Cesium Ions in a Proton-Conducting Zwitterionic Metal–Organic Framework

      Sorout Shalini, Shubhangi Aggarwal, Santosh K. Singh, Malvika Dutt, Thallaseril G. Ajithkumar and Ramanathan Vaidhyanathan

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/ejic.201600364

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      Partial replacement of protons from a zwitterionic pyridinol of a Mg(terephthalate) metal–organic framework by about 10 % Cs+ ions provides a 10000-fold enhancement in proton conductivity. The concentration of Cs+ needs to be optimal to realize this maximum enhancement.

    2. Silver Corroles

      Ligand Noninnocence in Silver Corroles: A XANES Investigation

      Ritimukta Sarangi, Logan J. Giles, Kolle E. Thomas and Abhik Ghosh

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/ejic.201600413

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      Silver L3 X-ray absorption spectroscopy has provided direct experimental support for variable innocent/noninnocent electronic structures among silver corroles.

  7. Full Papers

    1. Carbon Dioxide Reforming

      One-Pot Synthesis of Ordered Mesoporous NiSiAl Oxides for Catalyzing CO2 Reforming of CH4

      Xianmei Xiang, Huahua Zhao, Jian Yang, Jun Zhao, Liang Yan, Huanling Song and Lingjun Chou

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/ejic.201600463

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      Ordered mesoporous NiSiAl oxide is prepared by an improved evaporation-induced self-assembly strategy. The silica doping improves the retention of ordered mesopores and the amorphous NiAl phase; this permits the uniform dispersion of the active Ni nanoparticles and, thus, decreases the amount of deposited carbon and improves the catalytic stability for the CO2 reforming of CH4.

    2. Continuous Synthesis

      A Facile “Green” Route for Scalable Batch Production and Continuous Synthesis of Zirconium MOFs

      Helge Reinsch, Steve Waitschat, Sachin M. Chavan, Karl Petter Lillerud and Norbert Stock

      Version of Record online: 16 JUN 2016 | DOI: 10.1002/ejic.201600295

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      A “green” preparative route for the synthesis of zirconium MOFs with diverse topologies was developed. This allows the synthesis of multigram amounts in batch reactions or under continuous flow conditions.

    3. Silicon

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      Four-, Five-, and Six-Coordinate Silicon(IV) Complexes: Reactivity of the Donor-Stabilized Silylenes [iPrNC(Ph)NiPr]2Si and [iPrNC(NiPr2)NiPr]2Si Towards Me3SiN3 and PhSCH2N3

      Felix M. Mück, Bettina Förster, Johannes A. Baus, Marco Nutz, Christian Burschka, Rüdiger Bertermann and Reinhold Tacke

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/ejic.201600402

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      The donor-stabilized silylenes 1 and 2 react with Me3SiN3 to afford 3 and 4, respectively. Treatment of 1 with PhSCH2N3 affords 5 (a 1:1 mixture of diastereomers 5a and 5b).

    4. Isocorroles

      Template Synthesis of Alkyl-Substituted Metal Isocorroles

      Martin Hoffmann, Birte Cordes, Christian Kleeberg, Peter Schweyen, Benedikt Wolfram and Martin Bröring

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/ejic.201600419

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      Broken conjugation is the most noteworthy structural feature of isocorroles. The loss of aromaticity of this ring-contracted porphyrinoid results in intense NIR absorption bands. The gem-dimethyl substitution at the meso position ensures sufficient stability for these polyenic compounds, which form metal complexes of Ni, Cu, and Pd through different template-based synthetic protocols.

    5. Single-Ion Magnetism

      Field-Induced Single-Ion Magnetism Based on Spin-Phonon Relaxation in a Distorted Octahedral High-Spin Cobalt(II) Complex

      Ryuta Ishikawa, Yoji Horii, Ryo Nakanishi, Shunya Ueno, Brian K. Breedlove, Masahiro Yamashita and Satoshi Kawata

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/ejic.201600481

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      A six-coordinate mononuclear high-spin CoII complex with large positive axial and significant rhombic zero-field splittings exhibits slow magnetic relaxation in applied direct-current magnetic fields and is a field-induced single-ion magnet; in agreement with theoretical studies, spin relaxation occurs through two-phonon Raman and direct spin-phonon bottleneck processes of Kramers ions.

    6. Water Oxidation Catalysts

      Multifaceted Bicubane Co4 Clusters: Magnetism, Photocatalytic Oxygen Evolution, and Electrical Conductivity

      Wan-Feng Xie, Ling-Yu Guo, Jia-Heng Xu, Marko Jagodič, Zvonko Jagličić, Wen-Guang Wang, Gui-Lin Zhuang, Zhi Wang, Chen-Ho Tung and Di Sun

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/ejic.201600510

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      This work presents a new core type of cobalt cluster that possesses photocatalytic oxygen-evolution capabilities, provides new insight into the catalysis-related mechanism based on the relative oxygen evolution efficiency, and applies the iodine-doping strategy to boost the conductivity of cluster compounds.

  8. Microreviews

    1. Anti-Inflammatory Drugs

      Non-Steroidal Anti-Inflammatory Drugs (NSAIDs) in Metal Complexes and Their Effect at the Cellular Level

      Christina N. Banti and Sotiris K. Hadjikakou

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/ejic.201501480

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      The nonsteroidal anti-inflammatory drugs (NSAIDs) make up a great group of drugs that offer benefits in the prevention of various cancers. Coordinated metal ions with NSAIDs provide advantages over the drugs themselves. This review focuses on the antibacterial and antiproliferative activities of metal complexes of NSAIDs.

  9. Full Papers

    1. Nonplanar Hemes

      Spin Modulation in Highly Distorted FeIII Porphyrinates by Using Axial Coordination and Their π-Cation Radicals

      Dipankar Sahoo, Tapas Guchhait and Sankar Prasad Rath

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/ejic.201600255

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      A series of five-coordinate FeIII octaaryltetraphenylporphyrins with varying axial ligand field strength and their 1 e-oxidized complexes have been synthesized and characterized. The molecular structures and their spectroscopic properties including metal spins have been scrutinized.

    2. Carbon Dioxide Capture

      Quantitative Structure–Property Relationship Models for Recognizing Metal Organic Frameworks (MOFs) with High CO2 Working Capacity and CO2/CH4 Selectivity for Methane Purification

      Mohammad Zein Aghaji, Michael Fernandez, Peter G. Boyd, Thomas D. Daff and Tom K. Woo

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/ejic.201600365

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      Robust machine learning QSPR models have been developed to accurately recognize high-performing metal organic framework materials for both the working capacity and selectivity in CO2/CH4 gas separations under methane purification conditions. The models were trained on 32,500 MOFs and validated on a test set of ca. 290,000 hypothetical MOFs.

    3. Water Oxidation

      Mononuclear Iron Complexes with Tetraazadentate Ligands as Water Oxidation Catalysts

      Gayatri Panchbhai, Wangkheimayum Marjit Singh, Biswanath Das, Reuben T. Jane and Anders Thapper

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/ejic.201600165

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      Two iron(II) complexes with tetraazadentate ligands are synthesized, characterized and reported as molecular water oxidation catalysts when using cerium(IV) as a chemical oxidant.

  10. Communications

    1. Mixed–Matrix Membranes

      Increased Selectivity in CO2/CH4 Separation with Mixed-Matrix Membranes of Polysulfone and Mixed-MOFs MIL-101(Cr) and ZIF-8

      Harold B. Tanh Jeazet, Sara Sorribas, José M. Román-Marín, Beatriz Zornoza, Carlos Téllez, Joaquín Coronas and Christoph Janiak

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/ejic.201600190

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      Combination of two different MOFs [MIL-101(Cr) and ZIF-8] in the same MMM produces synergy effects with significant increase of CO2/CH4 selectivity compared to analogous MMMs with only one filler type.

  11. Full Papers

    1. Structural Analysis

      Structure Elucidation of an Yttrium Diethyldithiocarbamato-Phenanthroline Complex by X-ray Crystallography, Solid-State NMR, and ab-initio Quantum Chemical Calculations

      Vasantha Gowda, Bipul Sarma, Sven Öberg, Ville-Veikko Telkki, Anna-Carin Larsson, Perttu Lantto and Oleg N. Antzutkin

      Version of Record online: 14 JUN 2016 | DOI: 10.1002/ejic.201600059

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      A structural analysis method combining solid-state NMR, XRD and DFT calculations was used in elucidation of the molecular and electronic structure of [Y{S2CN(C2H5)2}3(1,10-Phenanthroline)]. An approximate structure was generated by replacing the Nd3+ with Y3+ in the known structure of [Nd{S2CN(C2H5)2}3PHEN] and then subjected to first principles quantum chemical geometry optimisation using periodic DFT method.

    2. Metal–Organic Frameworks

      Synthesis and Structural Characterization of a Two-Dimensional Magnesium Acetate, Mg7(OH)2(OAc)12(H2O)4·4H2O, a Precursor to Three-Dimensional Porous Magnesium Acetate

      Qi Shi, Youjun Guan, Fei Wang, Jiangfeng Yang, Libo Li, Jinping Li, Jinxiang Dong and Fa-Nian Shi

      Version of Record online: 14 JUN 2016 | DOI: 10.1002/ejic.201600249

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      A new 2D magnesium acetate, Mg7(OH)2(OAc)12(H2O)4·4H2O, was obtained from zero-dimensional magnesium acetate tetrahydrate as a single source of the metal and carboxylate ions with nonpolar benzene as the solvent. Mg7(OH)2(OAc)12(H2O)4·4H2O exhibits an unusual 2D inorganic [Mg7(OH)2(O)23(H2O)4]n subnetwork and converts into 3D porous magnesium acetate at 250 °C in air.

  12. Communications

    1. Tuning of MOF Synthesis

      Modulated Synthesis of Metal-Organic Frameworks through Tuning of the Initial Oxidation State of the Metal

      Mathieu Bosch, Xing Sun, Shuai Yuan, Ying-Pin Chen, Qi Wang, Xuan Wang and Hong-Cai Zhou

      Version of Record online: 10 JUN 2016 | DOI: 10.1002/ejic.201600211

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      In this work, we introduce a new method for the tuning of MOF synthesis: modulation through alteration of the metal source's initial oxidation state. This concept is demonstrated through the synthesis of PCN-47, PCN-48, and PCN-49, MOFs with distinct structures and porosities synthesized from the same metal and ligand with the metal initially in different oxidation states.

  13. Full Papers

    1. Proton-Conducting MOFs

      Proton Conductivities Manipulated by the Counter-Anions in 2D Co-Ca Coordination Frameworks

      Song-Song Bao, Yu-Xuan Wu, Nan-Zhu Li and Li-Min Zheng

      Version of Record online: 10 JUN 2016 | DOI: 10.1002/ejic.201600203

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      This work provides a new route to enhance proton conductivities of metal-organic framework materials by tuning the size, shapes and hydrogen-bonding capabilities of the counter-anions.

  14. Communications

    1. Piezoelectric Perovskites

      High Energy Density Lead-Free Piezoelectric Ceramics for Energy Harvesting and Derived from a Sol–Gel Route

      Mupeng Zheng, Yudong Hou, Lina Zhang and Mankang Zhu

      Version of Record online: 10 JUN 2016 | DOI: 10.1002/ejic.201600279

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      The (Na0.5K0.5)0.94Li0.06NbO3 powder derived from a sol–gel route is free of hard agglomeration and consists of similar quadrate nanosheets with an average size of 30 nm. Niobate ceramics with a high energy density are constructed from these nanoprecursor powders, and they show potential application in new-generation lead-free piezoelectric energy harvesters.

    2. Thermochromism

      Anomalous Thermal Expansion and Luminescence Thermochromism in Silver(I) Dicyanamide

      Sarah A. Hodgson, Sarah J. Hunt, Thomas Just Sørensen, Amber L. Thompson, Emily M. Reynolds, Stephen Faulkner and Andrew L. Goodwin

      Version of Record online: 10 JUN 2016 | DOI: 10.1002/ejic.201600246

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      Silver(I) dicyanamide exhibits both mechanical and optical sensitivity to temperature. This responsive metal–organic framework may find application in high-precision temperature sensors.

  15. Full Papers

    1. Boron-Based Sensors

      11B NMR/MRI Sensing of Copper(II) Ions In Vitro by the Decomposition of a Hybrid Compound of a nido-o-Carborane and a Metal Chelator

      Tomohiro Tanaka, Rikita Araki, Takaomi Saido, Ryo Abe and Shin Aoki

      Version of Record online: 10 JUN 2016 | DOI: 10.1002/ejic.201600346

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      A hybrid molecule made up of a nido-o-carborane and a metal chelator decomposes rapidly in the presence of Cu2+ under mild conditions. This probe is useful for the 11B NMR/MRI sensing of Cu2+ in vitro.

    2. Single-Molecule Magnets

      Hydrazone-Ligand-Based Homodinuclear Lanthanide Complexes: Synthesis, Structure, and Magnetism

      Sourav Biswas, Sourav Das, Guillaume Rogez and Vadapalli Chandrasekhar

      Version of Record online: 10 JUN 2016 | DOI: 10.1002/ejic.201600335

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      The reaction of the multidentate semiflexible ligand N′-(2-hydroxy-3-methoxybenzylidene)acetohydrazide with appropriate lanthanide salts in the presence of pivalic acid fostered the dinuclear complexes [Ln2(LH)22-Piv-κ2O,O′)2(NO32O,O′)2] [Ln = DyIII (1), TbIII (2), GdIII (3), and HoIII (4)]. Detailed magnetic analysis revealed the presence of SMM behavior in 1 with an energy barrier of 40 K.

    3. Noble Gas Chemistry

      Influence of the Increasing Size of the M2+ Cation on the Crystal Structures of XeF5M(SbF6)3 (M = Ni, Mg, Cu, Zn, Co, Mn, Pd) and (XeF5)3[Hg(HF)]2(SbF6)7

      Zoran Mazej and Evgeny Goreshnik

      Version of Record online: 10 JUN 2016 | DOI: 10.1002/ejic.201600317

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      Three-dimensional [M(SbF6)3] (M2+ = Ni < Mg < Cu < Zn < Co < Mn < Pd) frameworks built of M2+ cations interconnected by SbF6 octahedra, forming in this way cavities within which the [XeF5]+ ions are located, are shown to be energetically favorable for XeF5M(SbF6)3 compounds. A different composition was obtained for the much larger Hg2+ cation, that is, (XeF5)3[Hg(HF)](SbF6)7.

  16. Microreviews

    1. “Green” Synthesis

      “Green” Synthesis of Metal-Organic Frameworks

      Helge Reinsch

      Version of Record online: 9 JUN 2016 | DOI: 10.1002/ejic.201600286

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      During the recent years the research in the field of MOFs has gradually shifted towards a focus on more sustainable and industrially feasible conditions. This microreview gives several concise examples from this emerging field of research and also depicts some perspectives.

  17. Full Papers

    1. Magnetite Nanoparticles

      Redox Properties on the Surfaces of Silica Networks Encapsulating Clusters of Superparamagnetic Magnetite Nanoparticles

      The Son Le, Young-Seon Ko, Vandung Do, Won Il Cho and Kyoungja Woo

      Version of Record online: 9 JUN 2016 | DOI: 10.1002/ejic.201501460

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      Clusters of superparamagnetic Fe3O4 nanoparticles encapsulated by silica of different thicknesses play a role not only as a magnetically collectable supporter but also as a reducing agent, showing effects on the silica surface up to over about 100 nm, quite a long distance, through the porous silica networks.

    2. Lanthanide Borates

      Synthesis, Single-Crystal Structure Determination, and Vibrational Spectroscopy of the Europium Borate Eu[B6O8(OH)5]·H3BO3

      Teresa S. Ortner, Klaus Wurst, Markus Seibald, Bastian Joachim and Hubert Huppertz

      Version of Record online: 9 JUN 2016 | DOI: 10.1002/ejic.201600222

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      The first europium borate showing a hexaborate structure and isolated boric acid groups was obtained by hydrothermal synthesis. Its crystal structure, vibrational spectroscopic, and luminescence properties were elucidated.

    3. Silanes

      Dehydrogenative Coupling of a Tertiary Silane Using Wilkinson's Catalyst

      Susan Azpeitia, Belén Fernández, María A. Garralda and Miguel A. Huertos

      Version of Record online: 9 JUN 2016 | DOI: 10.1002/ejic.201600395

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      Wilkinson's catalyst results active in the dehydrogenative coupling of the tertiary silane SiMeH(o-C6H4SMe)2 to give (o-C6H4SMe)2MeSi–SiMe(o-C6H4SMe)2. The stoichiometric reaction of [Rh(PPh3)3Cl] with the substrate affords a silyl-hydrido-RhIII complex, which is an active specie in the catalytic process.

    4. Pd Nanoparticles

      In-Situ TEM on Epitaxial and Non-Epitaxial Oxidation of Pd and Reduction of PdO at P = 0.2–0.7 bar and T = 20–650 °C

      Tadahiro Yokosawa, Frans D. Tichelaar and Henny W. Zandbergen

      Version of Record online: 8 JUN 2016 | DOI: 10.1002/ejic.201501353

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      Pd nanoparticles act as catalysts to remove NOx in car exhaust gasses via enhanced oxidation and reduction. Oxidation of Pd and reduction of PdO are studied on the nano scale using in-situ TEM techniques at realistic gas pressures and temperatures, giving new insights into crystallographic details of these phase transistions.

    5. Glucose Sensing

      Fast Synthesis of Hierarchical Co(OH)2 Nanosheet Hollow Spheres with Enhanced Glucose Sensing

      Chufeng Xu, Yang Cao, Yong Chen, Wei Huang, Delun Chen, Qingyou Huang and Jinchun Tu

      Version of Record online: 8 JUN 2016 | DOI: 10.1002/ejic.201600298

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      Hierarchical Co(OH)2 hollow spheres composed of nanosheets are synthesized by fast etching of polycrystalline cuprous oxide and are used for the nonenzymatic electrochemical detection of glucose. The shell structure of the hierarchical Co(OH)2 nanosheet hollow spheres is about 50 nm thick, and the sensor shows a high sensitivity of 925.21 µA mm–1 cm–2 and a detection limit of 0.93 µm.

    6. Halogenated Ligands

      Effects of Ligand Halogenation on the Electron Localization, Geometry and Spin State of Low-Coordinate (β-Diketiminato)iron Complexes

      Sarina M. Bellows, William W. Brennessel and Patrick L. Holland

      Version of Record online: 30 MAY 2016 | DOI: 10.1002/ejic.201600112

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      We present a new halogenated version of a β-diketiminato ligand, which has fluoro and chloro substituents. An iron(II) complex can be reduced in situ to react with adamantyl azide to give tetrazene complexes and with isocyanides to give organometallic complexes. The electronic and steric impact of the new ligand is elucidated using structure analysis, spectroscopy, and computations.

    7. MOF Polymer Membranes

      Luminescent Metal–Organic Framework Mixed-Matrix Membranes from Lanthanide Metal–Organic Frameworks in Polysulfone and Matrimid

      Janina Dechnik, Friedrich Mühlbach, Dennis Dietrich, Tobias Wehner, Marcus Gutmann, Tessa Lühmann, Lorenz Meinel, Christoph Janiak and Klaus Müller-Buschbaum

      Version of Record online: 30 MAY 2016 | DOI: 10.1002/ejic.201600235

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      The luminescent metal–organic framework/polymer (MOF–polymer) mixed-matrix membranes 3[Sr0.9Eu0.1Im2]@PSF (Im = imidazolate, PSF = polysulfone), 3[Sr0.9Eu0.1Im2]@Matrimid, and 2[Tb2Cl6(bipy)3]·2bipy@PSF (bipy = 4,4-bipyridine) are prepared with the polysulfone Ultrasonî S and Matrimidî. Thereby, MOF luminescence can be maintained and transferred into processable polymer membranes.

    8. Iron(III) Porphyrins

      Binuclear Highly Distorted Iron(III) Porphyrins Bridged by the Dianions of Hydroquinones: Role of the Bridge in Electronic Communication

      Dipankar Sahoo, Akhil Kumar Singh and Sankar Prasad Rath

      Version of Record online: 30 MAY 2016 | DOI: 10.1002/ejic.201600257

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      A family of binuclear highly substituted and distorted ferric porphyrins bridged through a variety of p-hydroquinone dianions is reported. The iron centres are involved in weak antiferromagnetic exchange interactions, the extent of which depends on the electronic nature of the bridge.

    9. Multifunctional Materials

      CoII and CuII Fluorescent Complexes with Acridine-Based Ligands

      Samira Gholizadeh Dogaheh, María José Heras Ojea, Lidia Rosado Piquer, Lluís Artús Suàrez, Hamid Khanmohammadi, Guillem Aromí and E. Carolina Sañudo

      Version of Record online: 30 MAY 2016 | DOI: 10.1002/ejic.201600297

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      Magnetic and optical materials are in the spotlight, where one can envision using light to switch the magnetic properties. This is relevant to fields as diverse as information storage, processing and molecular spintronics. In this paper we report the synthesis and characterization of new multifunctional magnetic and fluorescent complexes with a ligand based on the acridine group.

    10. Polyoxometalates

      A Vanadogermanate Dimer-Based Chain with Magnetic and Luminescent Properties

      Ning Li, Danfeng He, Ying Lu, Yiwei Liu, Li Xu, Xiahua Zhong, Zehong Guo and Shuxia Liu

      Version of Record online: 30 MAY 2016 | DOI: 10.1002/ejic.201600187

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      The first vanadogermanate-based dimer has been prepared hydrothermally and is constructed by two dicadmium-substituted {[Cd(en)2][Cd(en)]2Ge8V12O40(OH)8} cluster units and dinuclear {[Cd(en)(H2O)]2+}2 cations as linkages. Magnetic measurements indicate antiferromagnetic interactions between the VIV centers, and the compound exhibits intense blue luminescence in the solid state.

  18. Communication

    1. Sensitisers for DSSCs

      Hybrid Cyclometalated Iridium Coumarin Complex as a Sensitiser of Both n- and p-Type DSSCs

      Alessandro Sinopoli, Christopher J. Wood, Elizabeth A. Gibson and Paul I. P. Elliott

      Version of Record online: 30 MAY 2016 | DOI: 10.1002/ejic.201600242

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      A hybrid biscyclometalated couamrin/iridium complex, AS19, is presented, which exhibits intense visible absorption and sensitises both n- and p-type dye-sensitised solar cells (DSSCs).

  19. Full Papers

    1. ZnO–Clay Hybrids

      Efficient Photodegradation of Organics in Acidic Solution by ZnO–Smectite Hybrids

      Nuttaporn Khumchoo, Nithima Khaorapapong, Areeporn Ontam, Sonchai Intachai and Makoto Ogawa

      Version of Record online: 30 MAY 2016 | DOI: 10.1002/ejic.201600252

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      ZnO has been immobilized in the interlayer space of smectites (montmorillonite and saponite). The ZnO–smectites showed photocatalytic activity towards the degradation of Methylene Blue in aqueous acidic solution. The ZnO is stabilized by the interactions with the smectites.

    2. Chirality Inversion

      Kinetic Studies of the Chirality Inversion of Salicylaldiminato–Ruthenium Using Racemic η6-p-Cymene Complexes as a Mechanistic Probe

      Naruyoshi Komiya, Tomoko Nakajima, Masato Hotta, Takatoshi Maeda, Tatsuya Matsuoka, Soichiro Kawamorita and Takeshi Naota

      Version of Record online: 27 MAY 2016 | DOI: 10.1002/ejic.201600221

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      Kinetic studies of the chirality inversion of a series of mono- and bimetallic (p-cymene)(salicylaldiminato)RuII complexes with halo ligands in solution have been conducted by means of the line-shape method, using 1H NMR spectroscopy to evaluate the signal exchange rates between diastereotopic protons in the p-cymene ligand.

    3. Sodium-Ion Batteries

      High-Performance Na3V2(PO4)3/C Cathode for Sodium-Ion Batteries Prepared by a Ball-Milling-Assisted Method

      Rafael Klee, María José Aragón, Ricardo Alcántara, José L. Tirado and Pedro Lavela

      Version of Record online: 27 MAY 2016 | DOI: 10.1002/ejic.201600241

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      The synthesis of Na3V2(PO4)3/C by a wet-ball-milling and an in situ carbon-compositing process yields pure and crystalline composites with enlarged specific surface areas. This material reveals good performance as a cathode for sodium-ion batteries owing to its excellent kinetic response.

    4. Energetic Materials

      Oxalyl Chloride and Hydrazide Based Energetic Polynitro Derivatives

      Thomas M. Klapötke, Burkhard Krumm and Regina Scharf

      Version of Record online: 27 MAY 2016 | DOI: 10.1002/ejic.201600357

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      Several polynitro-substituted compounds derived from oxalyl chloride and hydrazide are synthesized, and their spectroscopic properties are studied. Their energetic properties are discussed in comparison with those of ammonium perchlorate as the typical oxidizer for solid rocket propulsion.

    5. Dendrimer Composites

      Silica Functionalized by Bifunctional Dendrimers: Hybrid Nanomaterials for Trapping CO2

      David Riegert, Laurianne Bareille, Régis Laurent, Jean-Pierre Majoral, Anne-Marie Caminade and Alexandra Chaumonnot

      Version of Record online: 27 MAY 2016 | DOI: 10.1002/ejic.201600426

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      Several types of bifunctional dendrimeric structures have been grafted to several types of nanoporous silica to afford various hybrid nanomaterials. Some of them have been used to trap CO2, with various efficiencies, depending on the size and shape of the dendrimeric structures and the porosity of the silicas.

  20. Communication

    1. Siloxanes

      Unexpected Selectivity in Cyclotetrasiloxane Formation by the Hydrolytic Condensation Reaction of Trichloro(phenyl)silane

      Fujio Yagihashi, Masayasu Igarashi, Yumiko Nakajima, Kazuhiko Sato, Yoshiyuki Yumoto, Chinami Matsui and Shigeru Shimada

      Version of Record online: 27 MAY 2016 | DOI: 10.1002/ejic.201600454

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      Selective cyclization: Hydrolytic condensation of PhSiCl3 in aqueous medium affords only three cyclic tetrasiloxane diastereomers out of four conceivable ones. This phenomenon can reasonably be explained by exclusive cyclization through the meso-linear-tetrasiloxane.

  21. Full Papers

    1. Tungsten Hexachloride Reactivity

      Reactivity of [WCl6] with Ethers: A Joint Computational, Spectroscopic and Crystallographic Study

      Marco Bortoluzzi, Fabio Marchetti, Guido Pampaloni and Stefano Zacchini

      Version of Record online: 27 MAY 2016 | DOI: 10.1002/ejic.201600308

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      The chemistry of tungsten hexachloride with a selection of alkyl and aryl ethers has been elucidated by means of analytical and spectroscopic techniques as well as by DFT calculations.

    2. Oxidation Catalysis

      Vanadium Aminophenolate Complexes and Their Catalytic Activity in Aerobic and H2O2-Mediated Oxidation Reactions

      Ali I. Elkurtehi, Andrew G. Walsh, Louise N. Dawe and Francesca M. Kerton

      Version of Record online: 27 MAY 2016 | DOI: 10.1002/ejic.201600068

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      The effects of ligand variation on homogeneous catalytic oxidative transformations of alcohols and ethers was investigated.

    3. Single-Molecule Magnets

      Cyclic Single-Molecule Magnets: From Even-Numbered Hexanuclear to Odd-Numbered Heptanuclear Dysprosium Clusters

      Haiquan Tian, Song-Song Bao and Li-Min Zheng

      Version of Record online: 27 MAY 2016 | DOI: 10.1002/ejic.201600392

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      Cyclic single-molecule magnets. By integrating single and double pyrazinyl hydrazone ligands in the presence of a phosphonic acid, noncentered cyclic Dy6 and Dy7 clusters have been isolated successfully. Both show single-molecule magnet behavior at low temperature.

    4. Calixarene Complexes

      Lanthanide Complexes of a Calix[4]arene Ligand with Dangling Phosphonate and Picolinamide Arms: Synthesis, Crystal Structures, and Extraction Properties

      Florian Glasneck, Karolin Kobalz and Berthold Kersting

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/ejic.201600043

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      A preorganized calix[4]arene ligand with dangling phosphonate ester and picolinamide side arms forms stable 1:1 complexes with LaIII, PrIII, EuIII, GdIII, and YbIII. The lipophilic calixarene scaffold also enables extraction of lanthanum and europium picrates from aqueous solutions.

    5. Pd Catalysts

      Preparation of Secondary Phosphine Oxide Ligands through Nucleophilic Attack on Imines and Their Applications in Palladium-Catalyzed Catellani Reactions

      Chan-Yu Hu, Ya-Qian Chen, Guan-Yu Lin, Ming-Kai Huang, Yu-Chang Chang and Fung-E Hong

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/ejic.201600181

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      Several new secondary phosphine oxide (SPO) type ligands, 3a3n, were prepared. In addition, some SPOs as well as coordinated palladium complexes of ligand 3f, that is, 7fa, 7fb, and 8f, with fascinating bonding modes were characterized by X-ray diffraction methods. Some of these ligands were chosen to assist in palladium-catalyzed Catellani reactions.

    6. Photocatalytic Nanocomposites

      Preparation of a Single-Walled Carbon Nanotube/Cd0.8Zn0.2S Nanocomposite and Its Enhanced Photocatalytic Hydrogen Production Activity

      Bosi Peng, Xiaojing Liu and Renjie Li

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/ejic.201600183

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      Single-walled carbon nanotube (SWCNT) and Cd0.8Zn0.2S nanocomposites are fabricated by a coprecipitation process with prefunctionalized SWCNTs as the starting material. The SWCNTs improve both the visible-light-induced activity and stability for H2 production of Cd0.8Zn0.2S, and the activity (632 µmol h–1) is ca. 1.40 times higher than that (451 µmol h–1) of Cd0.8Zn0.2S alone.

    7. Energetic Materials

      Correlating the Structural, Electronic, and Explosive Sensitivity Properties of CuII Tetrazine Complexes

      Thomas W. Myers, Kathryn E. Brown, David E. Chavez, R. Jason Scharff and Jacqueline M. Veauthier

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/ejic.201600344

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      The coordination geometries and solid state packing properties influence the thermal stabilities, and mechanical sensitivities of new CuII tetrazine-based explosive complexes.

    8. Oligogermanes

      Photodecompostion of the Oligogermanes nBu3GeGePh2GenBu3 and nBu3GeGePh3: Identification of the Photoproducts by Spectroscopic and Spectrometric Methods

      Sangeetha P. Komanduri, Aaron C. Schrick, Christa L. Feasley, Craig P. Dufresne and Charles S. Weinert

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/ejic.201600421

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      Photolysis of a trigermane and digermane results in homolytic scission of the germanium–germanium bonds in these molecules to yield germanium radicals and germylenes.

    9. Rare-Earth Chemistry

      You have full text access to this OnlineOpen article
      Scandium Complexes Bearing Bis(oxazolinylphenyl)amide Ligands: An Analysis of Their Reactivity, Solution-State Structures and Photophysical Properties

      Stacey D. Bennett, Simon J. A. Pope, Robert L. Jenkins and Benjamin D. Ward

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/ejic.201600223

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      We report on the coordination chemistry of scandium bearing bis(oxazolinylphenyl)amide (BOPA) ligands. These complexes exist in two isomeric forms and have been characterised using luminescence spectroscopy. Stoichiometric reactions have been probed, showing the scope and limitations of the chemistry of oxazoline-bearing organometallic-type complexes.

    10. H-Bonding in Enzymes

      Unexpected Reaction Promoted by NH+···O=Mo Hydrogen Bonds in Nonpolar Solvents

      Taka-aki Okamura, Takayoshi Yamada, Yuki Hasenaka, Satoshi Yamashita and Kiyotaka Onitsuka

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/ejic.201600081

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      Tertiary ammonium salts of monooxomolybdenum(IV) benzenedithiolates containing bulky hydrophobic acylamino substituents were synthesised. In toluene, the NH+···O=Mo hydrogen bond unexpectedly promoted one-electron oxidation to MoV species by 2,6-lutidinium ion or 0.5 equiv. Me3NO, although normal oxygen atom transfer (OAT) was observed in polar solvents.

    11. Spin Crossover Compounds

      Cooperative High-Temperature Spin Crossover Accompanied by a Highly Anisotropic Structural Distortion

      Il'ya A. Gural'skiy, Bohdan O. Golub, Sergii I. Shylin, Vadim Ksenofontov, Helena J. Shepherd, Paul R. Raithby, Wolfgang Tremel and Igor O. Fritsky

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/ejic.201600406

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      A new 3D cyanoheterometallic framework, [Fe(pz){Au(CN)2}2], displays a highly cooperative spin crossover at elevated temperatures. The low-spin-to-high-spin transition induces a drastic structural distortion that involves a large one-directional expansion (10.6 %) and contraction (9.6 %) of the lattice.

    12. Tuning of Perovskites

      Wide-Range Tuning of the Mo Oxidation State in La1–xSrxFe2/3Mo1/3O3 Perovskites

      Sergey Ya. Istomin, Varvara V. Chernova, Evgeny V. Antipov, Maxim V. Lobanov, Ivan A. Bobrikov, Viktor Yu. Yushankhai, Anatoly M. Balagurov, K. Y. Hsu, J. -Y. Lin, J. M. Chen, J. F. Lee, Olga S. Volkova and Alexander N. Vasiliev

      Version of Record online: 18 MAY 2016 | DOI: 10.1002/ejic.201600020

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      La1–xSrxFe2/3Mo1/3O3 perovskites allow wide tuning of the Mo oxidation state from +3 (x = 0) to +6 (x = 1) with the FeIII oxidation state virtually unchanged. The magnetic properties vary between antiferromagnetic (AFM) for x = 0 to ferromagnetic (FIM) for x = 1.0.

    13. Superheavy Compounds

      The Valence States of Copernicium and Flerovium

      Abhik Ghosh and Jeanet Conradie

      Version of Record online: 18 MAY 2016 | DOI: 10.1002/ejic.201600146

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      Relativistic DFT calculations indicate that copernicium tetrafluoride should be substantially more stable than HgF4. Tetravalent flerovium on the other hand is unlikely to be experimentally accessible. Less noble than xenon, flerovium is predicted to yield both FlF2 and FlCl2 as stable molecules.

    14. MOFs and Sensors

      A Three-Dimensional Tetraphenylíethene-Based Metal–Organic Framework for Selective Gas Separation and Luminescence Sensing of Metal Ions

      Wei Yang, Ganggang Chang, Hailong Wang, Tong-Liang Hu, Zizhu Yao, Khalid Alfooty, Shengchang Xiang and Banglin Chen

      Version of Record online: 18 MAY 2016 | DOI: 10.1002/ejic.201600201

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      A three-dimensional multifunctional metal–organic framework (MOF), UTSA-86, made up of cadmium ions and a tetraphenylethene-based tetracarboxylate ligand has been synthesized and characterized by single-crystal X-ray diffraction analysis. This MOF exhibits permanent porosity, selective gas uptake, and luminescence sensing of metal ions.

    15. Low-Coordinate Cd Complexes

      (β-Diketiminato)cadmium Bis(trimethylsilyl)amide: Facile Access to Low-Coordinate Cadmium Complexes

      Elliot S. Borren, Christopher M. Fitchett and J. Robin Fulton

      Version of Record online: 18 MAY 2016 | DOI: 10.1002/ejic.201600274

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      [(BDI)Cd(HMDS)] is shown to be a useful synthon in the synthesis of low-coordinate (β-diketiminato)cadmium complexes, including terminal (aryloxo)- and (anilido)cadmium complexes. An elusive homometallic (β-diketiminato)cadmium halide complex was also generated (halide = chloride).

    16. Zintl Phases

      On the Extended Series of Quaternary Zintl Phases Ca13REMnSb11 (RE = La–Nd, Sm, Gd–Dy)

      Jai Prakash, Stanislav Stoyko, Leonard Voss and Svilen Bobev

      Version of Record online: 18 MAY 2016 | DOI: 10.1002/ejic.201600306

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      A new series of quaternary compounds with a general formula of Ca14–xRExMnSb11 (RE = La–Nd, Sm, Gd–Dy; x ≈ 1) were synthesized, and their crystal structures, electrical, and magnetic properties were investigated

    17. Ratiometric Thermometers

      Ratiometric Thermometer Based on a Lanthanoid Coordination Polymer

      Xue Liu, Maxime A. Siegler and Elisabeth Bouwman

      Version of Record online: 18 MAY 2016 | DOI: 10.1002/ejic.201600141

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      The mixed lanthanoid coordination polymer {[La0.95Tb0.05HL(H2O)2]·H2O}n (H4L = 5-hydroxy-1,2,4-benzenetricarboxylic acid) was prepared and fully characterized. This compound can be used as a ratiometric thermometer based on the emission intensity ratio of ligand phosphorescence and TbIII luminescence over the temperature range 90–280 K with a relative sensitivity of up to 0.53 % K–1.

    18. Enantiopure Iridium Complexes

      Proline and α-Methylproline as Chiral Auxiliaries for the Synthesis of Enantiopure Bis-Cyclometalated Iridium(III) Complexes

      Melanie Helms, Chuanyong Wang, Barbara Orth, Klaus Harms and Eric Meggers

      Version of Record online: 18 MAY 2016 | DOI: 10.1002/ejic.201600260

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      Proline and α-methylproline are very suitable chiral auxiliaries for the synthesis of enantiopure bis-cyclometalated iridium(III) complexes in a straightforward and convenient fashion without the tedious chromatographic separation of the intermediate diastereomers.

  22. Microreviews

    1. Phosphonate MOFs

      Robust Metal-Organic Frameworks Based on Tritopic Phosphonoaromatic Ligands

      Marco Taddei, Ferdinando Costantino and Riccardo Vivani

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/ejic.201600207

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      Tritopic phosphonoaromatic ligands have recently been used with the aim of synthesizing microporous compounds. The most relevant results are reviewed.

  23. Full Papers

    1. Coordination Polymers

      Vibrational–Structural Combined Study into Luminescent Mixed Copper(I)/Copper(II) Cyanide Coordination Polymers

      Francesca Grifasi, Emanuele Priola, Michele R. Chierotti, Eliano Diana, Claudio Garino and Roberto Gobetto

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/ejic.201600124

      Thumbnail image of graphical abstract

      A series of CuCN-based coordination polymers are characterized by single-crystal XRD, IR spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Luminescence measurements indicate that these substances are promising photoactive materials. We aims to establish a relationship between the crystal structure and emission pathways of this class of compounds.

    2. Emissive Cu Complexes

      Synthesis, Structure, and Characterization of Emissive Neutral Dinuclear CuI Complexes with a Tetraphosphane Bridging Ligand

      Jin Chen, Teng Teng, Jin-Yun Wang, Liju Kang, Xu-Lin Chen, Liang-Jin Xu, Rongmin Yu and Can-Zhong Lu

      Version of Record online: 13 MAY 2016 | DOI: 10.1002/ejic.201600030

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      Three neutral dinuclear CuI complexes with a tetraphosphane bridging ligand have been synthesized. The emissive properties at 298 and 77 K as well as theoretical studies point to thermally activated delayed fluorescence (TADF).

    3. Bionanoparticles

      Receptor-Targeted Luminescent Silver Bionanoparticles

      Anton Bunschoten, Patrick T. K. Chin, Tessa Buckle, Marte van der Linden, Arjan Barendregt, Marcel A. Verheijen and Fijs W. B. van Leeuwen

      Version of Record online: 13 MAY 2016 | DOI: 10.1002/ejic.201501414

      Thumbnail image of graphical abstract

      Luminescent silver nanoclusters can be encapsulated by human serum albumin, resulting in improved optical properties. This protein scaffold can be further functionalized with targeting moieties, resulting in HSA-Ag nanoparticles that can be applied as targeted imaging agents and possibly even as theranostic agents.

    4. NLO Complexes

      Side-Chain Metallopolymers Containing Second-Order NLO-Active Bimetallic NiII and PdII Schiff-Base Complexes: Syntheses, Structures, Electrochemical and Computational Studies

      Salvador Celedón, Mauricio Fuentealba, Thierry Roisnel, Isabelle Ledoux-Rak, Jean-René Hamon, David Carrillo and Carolina Manzur

      Version of Record online: 28 APR 2016 | DOI: 10.1002/ejic.201600236

      Thumbnail image of graphical abstract

      The redox active heterobimetallic subunits and their derived side-chain metallopolymer Schiff-base compounds exhibit good thermal stability and high second-order NLO responses. The electronic structure of the bimetallic species is analyzed by DFT and TD-DFT calculations.

  24. Communications

    1. Carbon Dioxide Fixation

      Anionic Metal–Organic Framework for Selective Dye Removal and CO2 Fixation

      Sanjay Kumar, Gaurav Verma, Wen-Yang Gao, Zheng Niu, Lukasz Wojtas and Shengqian Ma

      Version of Record online: 27 APR 2016 | DOI: 10.1002/ejic.201600218

      Thumbnail image of graphical abstract

      A microporous Zn-based anionic metal–organic framework (MOF) is synthesized with triangular 4,4′,4″-(pyridine-2,4,6-triyl)tribenzoic acid; it features open channels and proves to be a good capturing agent for cationic dyes. In addition, the Zn-MOF demonstrates excellent catalytic activity for CO2 fixation by cycloaddition reaction with epoxides.

  25. Full Papers

    1. Magnetic Metallogrids

      Expansion of a Discrete [3 × 3] Mn9 Metallogrid to a µ-Carboxylato-­Bridged Polymeric {Mn11}n Assembly

      Avinash Lakma, Sayed Muktar Hossain, Rabindra Nath Pradhan, Dinesh Topwal, Andrea Cornia and Akhilesh Kumar Singh

      Version of Record online: 27 APR 2016 | DOI: 10.1002/ejic.201600153

      Thumbnail image of graphical abstract

      Discrete and polymeric metallogrid compounds based on the [3 × 3] nonamanganese(II) square grid motif and featuring additional manganese(II) ions linked to the grid core were isolated. DC magnetic data show the successful expansion of the grid-type architectures based on tritopic bis(hydrazone) ligands appended with terminal pyruvate groups.

    2. Boron Liquid Crystals

      Polar Liquid Crystals Derived from Sulfonium Zwitterions of the [closo-1-CB11H12] Anion

      Jacek Pecyna, Remigiusz Żurawiński, Piotr Kaszyński, Damian Pociecha, Piotr Zagórski and Serhii Pakhomov

      Version of Record online: 27 APR 2016 | DOI: 10.1002/ejic.201600240

      Thumbnail image of graphical abstract

      Zwitterionic derivatives of the [closo-1-CB11H12] anion form liquid-crystalline phases and improve the dielectric properties of nematic liquid-crystal materials.

    3. Photoreactive Ru Complexes

      Highly DNA-Photoreactive Ruthen­ium 1,4,5,8-Tetraazaphenanthrene Complex Conjugated to the TAT Peptide: Efficient Vectorization inside HeLa Cells without Phototoxicity – The Importance of Cellular Distribution

      Lionel Marcélis, Sofia Kajouj, Jonathan Ghesquière, Gregory Fettweis, Isabelle Coupienne, Rémy Lartia, Mathieu Surin, Eric Defrancq, Jacques Piette, Cécile Moucheron and Andrée Kirsch-De Mesmaeker

      Version of Record online: 27 APR 2016 | DOI: 10.1002/ejic.201600278

      Thumbnail image of graphical abstract

      Photoreactive [Ru(TAP)2(phen)]2+ (TAP = 1,4,5,8-tetraazaphenanthrene; phen = 1,10-phenanthroline) is tethered to the cell-penetrating peptide TAT. Despite its ability to form stable photoadducts with DNA and efficient transportation into the cells, no photocytotoxicity was observed. A possible origin of the inactivity of the TAT-conjugated [Ru(TAP)2(phen)]2+ under illumination is proposed.

    4. Organosilatranes

      Organosilatranes with Acylthiourea Derivatives – Metal-Ion Binding, Substituent-Dependent Sensitivity, and Prospects for the Fabrication of Magnetic Hybrids

      Gurjaspreet Singh and Sunita Rani

      Version of Record online: 26 APR 2016 | DOI: 10.1002/ejic.201600204

      Thumbnail image of graphical abstract

      Acylthiourea-tethered organosilatranes are synthesized by the coupling of carboxylic acids with (aminopropyl)silatrane through acyl isothiocyanates. These derivatives are probed for metal-ion sensing. One of the silatranes is further immobilized onto the surface of magnetic silica nanospheres, and the hybrid is characterized and tested for the adsorption of copper and lead ions.

    5. Coordination Polymer Sensors

      Adenine-Based Coordination Polymers: Synthesis, Structure, and Properties

      S. R. Sushrutha, Raghunandan Hota and Srinivasan Natarajan

      Version of Record online: 26 APR 2016 | DOI: 10.1002/ejic.201600111

      Thumbnail image of graphical abstract

      The synthesis and characterization of adenine-based coordination polymers are presented. The compounds exhibit significant quenching towards nitrophenolic analytes and Fe3+ ions in solution.

  26. Microreviews

    1. Stereogenic Silanes

      Recent Progress in Asymmetric Synthesis and Application of Difunctionalized Silicon-Stereogenic Silanes

      Jonathan O. Bauer and Carsten Strohmann

      Version of Record online: 26 APR 2016 | DOI: 10.1002/ejic.201600100

      Thumbnail image of graphical abstract

      Difunctionalized silicon-chiral silanes are an attractive class of building blocks. They open new possibilities in design and application of chirally modified compounds and shed light on substitution mechanisms at silicon. Here we review important developments during the last decades, focusing on our recent contributions in this field of research.

  27. Full Papers

    1. Porous MOFs

      Carboxylate–Hydrazone Mixed-Linker Metal–Organic Frameworks: Synthesis, Structure, and Selective Gas Adsorption

      Kornel Roztocki, Irena Senkovska, Stefan Kaskel and Dariusz Matoga

      Version of Record online: 21 APR 2016 | DOI: 10.1002/ejic.201600134

      Thumbnail image of graphical abstract

      Two metal–organic frameworks incorporating carboxylate and acylhydrazone moieties are constructed from 4-pyridinecarbaldehyde isonicotinoyl hydrazone (PCIH) and linear dicarboxylate [dcx = 1,4-benzene- (BDC) or 4,4′-biphenyldicarboxylate (BPDC)]. Interpenetrated pillar-layered [Zn2(dcx)2(PCIH)2] frameworks selectively adsorb CO2 over N2.

    2. Arsenic Remediation

      Fe3O4@MIL-101 – A Selective and Regenerable Adsorbent for the Removal of As Species from Water

      Karel Folens, Karen Leus, Nina Ricci Nicomel, Maria Meledina, Stuart Turner, Gustaaf Van Tendeloo, Gijs Du Laing and Pascal Van Der Voort

      Version of Record online: 21 APR 2016 | DOI: 10.1002/ejic.201600160

      Thumbnail image of graphical abstract

      MIL-101(Cr) serves as a host for the in situ synthesis of Fe3O4 nanoparticles. The resulting material shows excellent affinity towards AsIII and AsV species in water. Ca2+, Mg2+, and phosphate ions as well as natural organic matter do not affect the removal efficiency or selectivity. The structural integrity of the host is maintained during the adsorption and desorption process.

  28. Communications

    1. Supported Nanocatalysts

      High Catalytic Performance of MIL-101-Immobilized NiRu Alloy Nanoparticles towards the Hydrolytic Dehydrogenation of Ammonia Borane

      Sandipan Roy, Pradip Pachfule and Qiang Xu

      Version of Record online: 19 APR 2016 | DOI: 10.1002/ejic.201600180

      Thumbnail image of graphical abstract

      Ultrafine NiRu alloy nanoparticles are successfully immobilized in the pores of MIL-101 by the double-solvent method combined with the overwhelming reduction approach. The immobilized nanoparticles show high catalytic performance towards the hydrolytic dehydrogenation of ammonia borane.

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