European Journal of Inorganic Chemistry

Cover image for Vol. 2016 Issue 13‐14

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 - 114
  1. Full Papers

    1. 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.

    2. 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.

    3. 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.

    4. 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.

    5. 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.

  2. 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).

  3. 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.

  4. 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.

  5. 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.

  6. Communication

    1. Iron Sulfur Clusters

      Rational Synthesis of the Carbonylí(perthiolato)diiron [Fe2(S3CPh2)(CO)6] and Related Complexes

      Peihua Zhao, Danielle L. Gray and Thomas B. Rauchfuss

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/ejic.201600366

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      The photoaddition of Ph2CS to Fe2(S2)(CO)6 gives the rare diiron perthiolate Fe2(S3CPh2)(CO)6. Desulfurization of the perthiolate gives Fe2(S2CPh2)(CO)6. These simple reactions provide access to Fe-S-CO compounds that previously were difficult to prepare.

  7. Full Papers

    1. 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.

    2. Rare-Earth Chemistry

      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.

    3. 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.

    4. 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

      Thumbnail image of graphical abstract

      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.

    5. 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.

    6. 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.

    7. 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.

    8. 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).

    9. 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

    10. 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.

    11. 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.

  8. 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.

  9. 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

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      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. Iminosemiquinone Ligands

      Secondary Interactions versus Intramolecular π–π Interactions in CuII–Diradical Complexes

      Richa Rakshit and Chandan Mukherjee

      Version of Record online: 13 MAY 2016 | DOI: 10.1002/ejic.201600019

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      Secondary interactions between the CuII atom and the secondary coordination atoms of tethered groups in mononuclear diradical-containing CuII complexes determine the ground-state electronic configuration of the complex. These secondary interactions can be overcome by weak intramolecular π–π interactions.

    4. 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

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      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.

    5. Magnetic Cyanoferrates

      Structure-Property Relationships in Tricyanoferrate(III) Building Blocks and Trinuclear Cyanide-Bridged Complexes

      Yuanzhu Zhang, Uma P. Malik, Benjamin Quiggins, Hung Nguyen, Christopher C. Beedle, Alexey E. Kovalev, Rodolphe Clérac, Stephen Hill, Benjamin J. Bythell and Stephen M. Holmes

      Version of Record online: 13 MAY 2016 | DOI: 10.1002/ejic.201600199

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      The preparation, structures, and magnetic properties of a tricyanoferrate, [NEt4][(Tp*Me)Fe(CN)3] (2), and three trinuclear {FeIII2NiII} derivatives are described. High-field/frequency EPR data indicates significant g-anisotropy in 2 and considerable magnetic anisotropy in one {FeIII2NiII} complex (5).

  10. Microreviews

    1. Boron-Centered Scorpionates

      Boron-Centered Scorpionate-Type NHC-Based Ligands and Their Metal Complexes

      Carlo Santini, Marika Marinelli and Maura Pellei

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/ejic.201600133

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      The advances in the design and coordination chemistry of scorpionate-type poly(NHC)borate ligands are described, highlighting their topology, flexibility, donor properties, synthesis, and reactivity pathways. The structural and electronic properties of these ligands are compared and correlated with their chemistry, particularly that of the transition metals.

  11. Full Papers

    1. 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

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      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.

    2. Oxidation Catalysis

      Synthesis and Oxidation Catalysis of [Tris(oxazolinyl)borato]cobalt(II) Scorpionates

      Regina R. Reinig, Debabrata Mukherjee, Zachary B. Weinstein, Weiwei Xie, Toshia Albright, Benjamin Baird, Tristan S. Gray, Arkady Ellern, Gordon J. Miller, Arthur H. Winter, Sergey L. Bud'ko and Aaron D. Sadow

      Version of Record online: 28 APR 2016 | DOI: 10.1002/ejic.201600237

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      A series of high-spin [tris(oxazolinyl)borato]cobalt(II) scorpionate complexes are synthesized and characterized by X-ray diffraction and spectroscopic investigations. The bulk-phase purity of these complexes is verified by X-ray powder diffraction.

  12. 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

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      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.

  13. 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

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      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

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      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

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      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

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      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

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

    6. Supported Scorpionate Complexes

      Rapid Synthesis of a Functional Resin-Supported Scorpionate and Its Copper(I, II), Rhodium(I), and Chromium(III) Complexes

      Patrick J. Desrochers, Adam J. Pearce, T. Ryan Rogers and Jeremy S. Rodman

      Version of Record online: 26 APR 2016 | DOI: 10.1002/ejic.201501254

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      A microwave-assisted method is described for the rapid preparation of a heterogeneous resin-supported scorpionate as its sodium salt. Formation of functional heterogeneous metal scorpionates was confirmed from subsequent reactions of its varied metal (Cr, Cu, Rh) complexes.

  14. Communications

    1. Hydrosilylenes

      Reactivity of an N-Heterocyclic Carbene Stabilized Hydrosilylene ­towards a Ketone and CO2: Experimental and Theoretical Study

      Carsten Eisenhut, Nora C. Breit, Tibor Szilvási, Elisabeth Irran and Shigeyoshi Inoue

      Version of Record online: 26 APR 2016 | DOI: 10.1002/ejic.201600355

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      Reaction of an N-heterocyclic carbene stabilized hydrosilylene with benzophenone yields a bicyclic compound through C–C bond formation and transition-metal-free hydrosilylation. In contrast, the reaction of the same silylene with carbon dioxide affords a cis/trans-cyclotrisiloxane by oxygen transfer. Both reaction mechanisms are studied in detail by DFT calculations.

  15. 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

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      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.

  16. Full Papers

    1. Cytotoxic Carbene Complexes

      Selective Formation of cis-N-Heterocyclic Carbene-PtII-Pnictogen Complexes and in vitro Evaluation of Their Cytotoxic Activities toward Cancer Cells

      Mathilde Bouché, Georges Dahm, Aline Maisse-François, Thierry Achard and Stéphane Bellemin-Laponnaz

      Version of Record online: 26 APR 2016 | DOI: 10.1002/ejic.201600296

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      We report on the synthesis of neutral and cationic heterotopic platinum complexes combining N-heterocyclic carbene (NHC) and pnictogen-based ligands.

    2. Tetradentate Ligands

      Coordination Chemistry of an Unsymmetrical Naphthyridine-Based Tetradentate Ligand toward Various Transition-Metal Ions

      Bing-Chen Tsai, Yi-Hung Liu, Shie-Ming Peng and Shiuh-Tzung Liu

      Version of Record online: 26 APR 2016 | DOI: 10.1002/ejic.201600163

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      Diruthenium, dinickel and dirhenium complexes containing an unsymmetrical ligand, 2-(2-pyridinyl)-7-(pyrazol-1-yl)-1,8-naphthyridine, were prepared and characterized. The nickel complex is an effective catalyst for the reduction of esters to the corresponding alcohols.

    3. Magnetic Lanthanide Complexes

      Tuning the Magnetoluminescence Behavior of Lanthanide Complexes Having Sphenocorona and Cubic Coordination Geometries

      Soumyabrata Goswami, Soumava Biswas, Kapil Tomar and Sanjit Konar

      Version of Record online: 26 APR 2016 | DOI: 10.1002/ejic.201600152

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      LnIII complexes (Ln = Dy, Ho, Tb) with distinctly different coordination geometries, namely, sphenocorona and cubic, are synthesized. The different coordination geometries around the LnIII centers significantly modulate the slow magnetic relaxation and photoluminescence behaviors of the complexes, as revealed from AC magnetic susceptibility and solid-state luminescence studies, respectively.

  17. Corrections

    1. You have free access to this content
  18. Full Papers

    1. PTA Gold Compounds

      Synthesis of Gold(I) Derivatives Bearing Alkylated 1,3,5-Triaza-7-phosphaadamantane as Selective Anticancer Metallodrugs

      Elena Atrián-Blasco, Sonia Gascón, M. Jesús Rodríguez-Yoldi, Mariano Laguna and Elena Cerrada

      Version of Record online: 24 APR 2016 | DOI: 10.1002/ejic.201600177

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      The preparation of new water-soluble mono- and bis-phosphanes derived from 1,3,5-triaza-7-phosphaadamantane (PTA) is described. Antiproliferative effects against colon cancer cell lines and low cytotoxicity towards differentiated cells (non-carcinogenic) have been observed for some of the gold complexes formed with these phosphanes.

    2. Coordination Polymers

      Paddlewheel-Type Dirhodium Tetrapivalate Based Coordination Polymer: Synthesis, Characterization, and Self-Assembly and Disassembly Transformation Properties

      Yusuke Kataoka, Natsumi Yano, Takashi Shimodaira, Yin-Nan Yan, Mikio Yamasaki, Hidekazu Tanaka, Kohji Omata, Tatsuya Kawamoto and Makoto Handa

      Version of Record online: 24 APR 2016 | DOI: 10.1002/ejic.201600197

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      An extended one-dimensional chain-type coordination polymer, [Rh2(piv)4(tpy)]n, has been obtained by solvothermal reaction of [Rh2(piv)4] and tpy in aqueous EtOH solution. This complex shows unique repeatable self-assembly and disassembly transformation properties in (aqueous) organic solvents.

    3. Oxidation Catalysts

      Synthesis, Characterization and ­Aerobic Alcohol Oxidation Catalysis of Palladium(II) Complexes with a Bis(imidazolyl)borate Ligand

      Kenta Ando, Jun Nakazawa and Shiro Hikichi

      Version of Record online: 24 APR 2016 | DOI: 10.1002/ejic.201600206

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      Chloro- and hydroxo-palladium(II) complexes containing the imidazole-based scorpionate ligand bis(1-methylimidazolyl)methylphenylborate, [B(ImN–Me)2MePh] (= LPh), have been synthesized. The hydroxo species can be converted into an active species that catalyzes secondary alcohol oxidation with O2 in the absence of base; the chlorido complex is inactive.

    4. Cage Compounds

      Double-Decker Coordination Cages

      Sreenivasulu Bandi, Sagarika Samantray, Rajan Deepan Chakravarthy, Amlan K. Pal, Garry S. Hanan and Dillip Kumar Chand

      Version of Record online: 24 APR 2016 | DOI: 10.1002/ejic.201600259

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      A trinuclear “double-decker” cage has been constructed from Pd(NO3)2 and a tridentate ligand. The NO3 counter anion acted as a template and was encapsulated into the cage structure. The encapsulated NO3 could be replaced by F, Cl, or Br but not by I. Excess NO3 did not harm the cages but excess Cl or Br destroyed the cages releasing the ligand.

    5. Amino Alcohol Ligands

      Systematic Synthesis of Di-, Tri-, and Tetranuclear Homo- and Heterometal Complexes Using a Mononuclear Copper Synthon with a Tetra­dentate Amino Alcohol Ligand

      Takayuki Nakajima, Chisako Yamashiro, Megumi Taya, Bunsho Kure and Tomoaki Tanase

      Version of Record online: 24 APR 2016 | DOI: 10.1002/ejic.201600142

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      A mononuclear copper complex bearing by an N2O2 tetradentate ligand is a suitable metalloligand for the systematic synthesis of di-, tri-, and tetranuclear homo- and heterometal complexes.

    6. Oxygen Activation

      Electronic Control of RuII Complexes with Proximal Oxophilic Phenylselenium Tethers: Synthesis, Characterization, and Activation of Molecular Oxygen

      Kaiji Shen, Haviv Ben-David, Alexander Laskavy, Gregory Leitus, Linda J. W. Simon and Ronny Neumann

      Version of Record online: 24 APR 2016 | DOI: 10.1002/ejic.201600123

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      Various ruthenium complexes with bipyridine or phenanthroline ligands with phenylselenium appendages react with molecular oxygen by oxygen–oxygen bond cleavage to form products with Ru–O–Se bonding motifs.

    7. Antibacterial Activity

      The Importance of Heterolepticity in Improving the Antibacterial Activity of Bismuth(III) Thiolates

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

      Version of Record online: 24 APR 2016 | DOI: 10.1002/ejic.201600076

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      Bismuth(III) mixed thiolato complexes [BiPh(5-MMTD)2{4-MMT(H)}] (1), [Bi(1-MMTZ)2{(PYM)(PYM(H))2}] (2), [Bi(MBT)2(5-MMTD)] (3), [Bi(4-BrMTD)3{2-MMI(H)}] (4) and [Bi(1-MMTZ)2{1-MMTZ(H)}(2-MMI){2-MMI(H)2}] (5) were synthesised, and their antibacterial activity was studied. Heteroleptic complexes seem to have improved activity.

  19. Communications

    1. (Alkylphosphanyl)boranes

      A Convenient Route to Monoalkyl-Substituted Phosphanylboranes (HRP–BH2–NMe3): Prospective Precursors to Poly[(alkylphosphino)­boranes]

      Andreas Stauber, Titel Jurca, Christian Marquardt, Martin Fleischmann, Michael Seidl, George R. Whittell, Ian Manners and Manfred Scheer

      Version of Record online: 24 APR 2016 | DOI: 10.1002/ejic.201600226

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      A route for the synthesis of monoalkyl-substituted Lewis-base-stabilized phosphinoboranes via borylphosphonium precursors is presented. Mild thermolysis of the Lewis-base-stabilized methylphosphinoborane generates the corresponding polymer consisting of at least 40 repeat units, which exemplifies the applicability of this method.

  20. 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

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      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. 3d–4f Heterometallic Clusters

      Synthesis, Characterization, Magnetic Properties, and Topological Aspects of Isoskeletal Heterometallic Hexanuclear CoII4LnIII2 Coordination Clusters Possessing 2,3,4M6–1 Topology

      Kieran Griffiths, Ghenadie Novitchi and George E. Kostakis

      Version of Record online: 21 APR 2016 | DOI: 10.1002/ejic.201600078

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      The use of a diprotic Schiff base ligand (H2L1) with Co(NO3)2 6H2O and LnCl3 x(H2O) afforded a family of hexanuclear coordination clusters formulated as [CoII4LnIII23-OH)2(L1)4Cl2(NO3)2(MeOH)4] 3(Et2O) where Ln is Y(1), Gd (2), Dy (3), and Tb (4). The topology of these compounds is 2,3,4M61. Compound 3 shows single molecule magnet (SMM) behavior.

    3. 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

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      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.

    4. Luminescent MOFs

      A Promising White-Light-Emitting Material Constructed from Encapsulating Eu3+/Tb3+ Hybrid Ions into a Robust Microporous Metal–Organic Framework

      Xuechuan Gao, Siyuan Chang, Houting Liu and Zhiliang Liu

      Version of Record online: 21 APR 2016 | DOI: 10.1002/ejic.201501431

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      A fascinating {[Zn(H2thca)0.5(tib)]·5H2O}n [H6thca = p-terphenyl-3,3′,3″,5,5′,5″-hexacarboxylic acid; tib = 1,3,5-tris(imidazolyl)benzene] metal–organic framework with a permanently porous structure and containing uncoordinated carboxyl groups within the pores is obtained. It emits blue light and can serve as a host for several guest Ln3+ cations; thus, it can exhibit broadband white emission by simple postmodification methods.

  21. Communications

    1. Alkali Metal Phosphates

      The Flexibility of P2O7 Dimers in Soft Structures: M2CdP2O7 (M = Rb, Cs)

      Xiaoyu Dong, Yunjing Shi, Mingjie Zhang, Zhaohui Chen, Qun Jing, Yun Yang, Shilie Pan, Zhihua Yang and Hongyi Li

      Version of Record online: 20 APR 2016 | DOI: 10.1002/ejic.201600086

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      Distortion of the P2O7 dimer in the Rb2CdP2O7 compound leads to a lower melting point than that of the Cs2CdP2O7 compound. It is found that the soft structures of Rb and Cs compounds can crystallize in different space groups.

  22. Full Papers

    1. Titanasilsesquioxane Catalysts

      Cyclopentadienyl–Silsesquioxane Titanium Catalysts: Factors Affecting Their Formation and Activity in Olefin Epoxidation with Aqueous Hydrogen Peroxide

      María Ventura, Vanessa Tabernero, Tomás Cuenca, Beatriz Royo and Gerardo Jiménez

      Version of Record online: 20 APR 2016 | DOI: 10.1002/ejic.201501474

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      A set of efficient catalysts based on titanium cyclopentadienyl–silsesquioxane derivatives for olefin epoxidation with aqueous hydrogen peroxide has been prepared. The modification of the electronic and steric properties of the Cp ring entails important differences in the chemical and catalytic behavior of such compounds

    2. Aluminium Hydrazides

      Reactivity of a Monomeric Aluminium Hydrazide towards Isocyanates and Isothiocyanates: Active Lewis Pair Behaviour versus Classical Insertion Reactions

      Werner Uhl, Julia Silissa Bruchhage, Matthias Willeke, Alexander Hepp and Jutta Kösters

      Version of Record online: 19 APR 2016 | DOI: 10.1002/ejic.201600170

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      A monomeric aluminium hydrazide with a strained AlN2 heterocycle was obtained by hydroalumination of a hydrazone. It shows interesting chemical behaviour and reacted as an active Lewis pair with the coordination of iBu2AlH or by insertion of one or two molecules of isocyanate into the Al–N polar covalent bond to afford a fascinating variety of structural motifs.

  23. Communications

    1. Metallocavitands

      Helical CuICuII3 Metallocavitands with Sulfur-Containing Schiff Base Ligands Exhibiting Ferromagnetic or Antiferromagnetic Interactions

      Asako Igashira-Kamiyama, Masayuki Saito, Shuntaro Kodera and Takumi Konno

      Version of Record online: 19 APR 2016 | DOI: 10.1002/ejic.201600290

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      Helical CuICuII3 metallocavitands were created by the one-pot reaction of D-penicillamine, salicylaldehydes, R3N, and CuII. Each metallocavitand is composed of three CuII square planes that form a cyclic wall capped with a CuI trigonal plane, accommodating an R3NH+ ion in its cavity. The magnetic behavior of the metallocavitands was altered by changing a substituent on the ligand.

    2. 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

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      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.

    3. Zintl Ion Ligands

      Introducing Tetrel Zintl Ions to N-Heterocyclic Carbenes – Synthesis of Coinage Metal NHC Complexes of [Ge9{Si(CH3)3}3]

      Felix S. Geitner and Thomas F. Fässler

      Version of Record online: 19 APR 2016 | DOI: 10.1002/ejic.201600258

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      Whereas intermetalloid cluster formation from ligand-free Zintl ions affords highly polar solvents, functionalized Zintl cluster anions allow for other solvents. Reactions with coinage metal N-heterocyclic carbene (NHC) complexes give a deep insight into the reactivity of Zintl clusters, as shown by the series [(η3-Ge9R3)M(NHCDipp)], M = Cu, Ag, Au and the subsequent transformation to [M(η3-Ge9R3)2][M(NHCDipp)2] for M = Ag.

  24. Full Papers

    1. Ionic Liquids

      Solvatochromic CuII-Containing Ionic Liquids with Ether Side Chains: Control of Solvent Response through Intramolecular Coordination

      Xue Lan, Hitoshi Hosokawa, Yusuke Funasako and Tomoyuki Mochida

      Version of Record online: 13 APR 2016 | DOI: 10.1002/ejic.201600188

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      Ionic liquids containing solvatochromic metal–chelate complexes with a flexible ether side chain have been synthesized. These salts exhibit vapochromic and solvatochromic properties. The side-chain coordination is released when solvents with coordination abilities stronger than that of the ether side chain are added.

    2. Soft Scorpionate Ligands

      Zinc Scorpionate Complexes with a Hybrid (Thiopyridazinyl)(thio­methimidazolyl)borate Ligand

      Michael Tüchler, Stefan Holler, Sarah Rendl, Natascha Stock, Ferdinand Belaj and Nadia C. Mösch-Zanetti

      Version of Record online: 13 APR 2016 | DOI: 10.1002/ejic.201501366

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      The mixed thiopyridazine/thiomethimidazole-containing soft scorpionate ligand (PnBm) was treated with zinc halide to form dimeric species. The bromine atoms can be abstracted with Tl(OTf) to form a triflate complex with a significantly short Zn–H–B distance.

  25. Microreviews

    1. Structural Variety

      Metal Complexes of Multitopic, Third Generation Poly(pyrazolyl)­methane Ligands: Multiple Coordination Arrangements

      Radu F. Semeniuc and Daniel L. Reger

      Version of Record online: 5 APR 2016 | DOI: 10.1002/ejic.201600116

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      Multitopic poly(pyrazolyl)methane ligands form metal complexes that show a variety of bonding modes and intricate overall structures.

  26. Full Papers

    1. Water-Soluble Complexes

      You have full text access to this OnlineOpen article
      Neutral 1,3,5-Triaza-7-phosphaadamantane-Ruthenium(II) Complexes as Precursors for the Preparation of Highly Water-Soluble Derivatives

      Federica Battistin, Gabriele Balducci, Elisabetta Iengo, Nicola Demitri and Enzo Alessio

      Version of Record online: 5 APR 2016 | DOI: 10.1002/ejic.201600084

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      We prepared precursors with one or more 1,3,5-triaza-7-phosphaadamantane (PTA) coligands for solubility and one or more labile ligands for facile replacement. The reactivity of trans- and cis-RuCl2(PTA)4 (1 and 2) and cis,cis,trans-RuCl2(dmso-S)2(PTA)2 (12, dmso = dimethyl sulfoxide) towards 2,2′-bipyridine (bpy), as a model diamine linker, is reported.

  27. Communications

    1. Carbon Dioxide Reduction

      A Rhenium-Functionalized Metal–Organic Framework as a Single-Site Catalyst for Photochemical Reduction of Carbon Dioxide

      Ruiyun Huang, Yu Peng, Cheng Wang, Zhan Shi and Wenbin Lin

      Version of Record online: 5 APR 2016 | DOI: 10.1002/ejic.201600064

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      A (bpy)Re(CO)3Cl-containing metal–organic framework (MOF) acts as an effective single-site catalyst to photochemically reduce carbon dioxide to carbon monoxide and formate. Mechanistic insights into the monomolecular pathway of the photocatalytic CO2 reduction have been obtained without interference from bimolecular pathways, thanks to site-isolation of the catalytic centers in MOFs.

  28. Microreviews

    1. Multiple-Metal Catalysis

      Multiple-Metal (De-)Hydrogenation-Catalysed Processes

      David Ventura-Espinosa and Jose A. Mata

      Version of Record online: 4 APR 2016 | DOI: 10.1002/ejic.201600090

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      Two or more metals acting together to accomplish difficult transformations. The unveiling of an old concept with modern potential applications in (de-)hydrogenation.

    2. Water-Soluble Complexes

      Water-Soluble C-Scorpionate Complexes – Catalytic and Biological Applications

      Luísa M. D. R. S. Martins and Armando J. L. Pombeiro

      Version of Record online: 31 MAR 2016 | DOI: 10.1002/ejic.201600053

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      Water-soluble carbon homoscorpionates and their coordination chemistry are reviewed. Moreover, the application of the resulting water-soluble tris(pyrazol-1-yl)methane metal complexes as catalysts for C–C bond formation and oxidative functionalization as well as their use as antiproliferative and antimicrobial agents are addressed.

  29. Communications

    1. Multimode Light Emission

      Multi-Mode White Light Emission in a ZnII Coordination Polymer from Excited-State Intramolecular Proton Transfer (ESIPT) Ligands

      Ling Chen, Cheng Yan, Mei Pan, Hai-Ping Wang, Ya-Nan Fan and Cheng-Yong Su

      Version of Record online: 30 MAR 2016 | DOI: 10.1002/ejic.201600089

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      ESIPT ligands were applied to assemble a ZnII coordination complex with solvent- and temperature-responsive single component white light emission.

  30. Microreviews

    1. Enzyme Models

      Scorpionate Complexes as Models for Molybdenum Enzymes

      Charles G. Young

      Version of Record online: 29 MAR 2016 | DOI: 10.1002/ejic.201501387

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      The study of molybdenum scorpionate complexes has greatly informed our understanding of the geometric and electronic structures, chemical and spectroscopic properties and mechanisms of action of Mo and W enzymes. This microreview focuses on the biologically relevant oxido- and sulfido-Mo(VI,V,IV) chemistry of hydrotris(R1/2-pyrazolyl)borate and related heteroscorpionate ligands.

  31. Full Papers

    1. Oxygen Atom Transfer

      Oxygen Atom Transfer Catalysis with Homogenous and Polymer-Supported N,N- and N,N,O-Heteroscorpionate Dioxidomolybdenum(VI) Complexes

      Tobias Paul, Philipp M. Rodehutskors, Jochen Schmidt and Nicolai Burzlaff

      Version of Record online: 21 MAR 2016 | DOI: 10.1002/ejic.201600026

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      The N,N-chelate ligand bdmvpzm and the N,N,O-heteroscorpionate ligand Hbdmvpza, both with vinyl linkers suitable for copolymerisation, are treated with [MoO2Cl2] to yield the molybdenum(VI) complexes [MoO2Cl2(bdmvpzm)] and [MoO2Cl(bdmvpza)]. The complexes and polymers with incorporated complexes are applied in oxygen-transfer studies.

  32. Communications

    1. Post-Synthetic Transformation

      SALE-Ing a MOF-Based “Ship of Theseus.” Sequential Building-Block Replacement for Complete Reformulation of a Pillared-Paddlewheel Metal-Organic Framework

      Yan Xu, Nicolaas A. Vermeulen, Yangyang Liu, Joseph T. Hupp and Omar K. Farha

      Version of Record online: 18 MAR 2016 | DOI: 10.1002/ejic.201600069

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      Text for Table of Contents: Interchange of a non-interpenetrating Zn based pillared-paddlewheel MOF into an entirely different Ni-based pillared-paddlewheel MOF has been achieved through the combination of solvent assisted linker exchange and transmetalation.

  33. Microreviews

    1. Pyridylborates

      Pyridylborates as a New Type of Robust Scorpionate Ligand: From Metal Complexes to Polymeric Materials

      Gajanan M. Pawar, John B. Sheridan and Frieder Jäkle

      Version of Record online: 17 MAR 2016 | DOI: 10.1002/ejic.201501373

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      An overview of the different classes of scorpionate ligands is provided, and an in-depth discussion of a new type of robust and tunable ligand, the tris(2-pyridyl)borates. The structure and synthesis of the ligands, key features of coordination with metal ions, the supramolecular crystal packing, transmetallation and applications in metallo-supramolecular polymer chemistry are addressed.

    2. Enzyme Modeling

      A Family of Homo- and Heteroscorpionate Ligands: Applications to Bioinorganic Chemistry

      Carl J. Carrano

      Version of Record online: 9 MAR 2016 | DOI: 10.1002/ejic.201501476

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      A family of heteroscorpionate ligands of the form N2X is presented where X can be interchanged between a thiolate sulfur, a pyrazole nitrogen, or a carboxylate, alkoxy or phenoxy oxygen in a series of isostructural isoelectronic metal complexes gives the bioinorganic chemist the ability to do the equivalent of “site directed mutagenesis”.

  34. Full Papers

    1. Bulky Tp Ligands

      Copper(I) Complexes of Naphthyl-Substituted Fluorinated Trispyr­azolylborate Ligands with Ethene and Carbon Monoxide

      Thomas F. van Dijkman, Maxime A. Siegler and Elisabeth Bouwman

      Version of Record online: 9 MAR 2016 | DOI: 10.1002/ejic.201600015

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      The structures of the CuI complexes of the two new ligands hydridotris[3-trifluoromethyl-5-(n-naphthyl)pyrazol-1-yl]borate (n = 1, [TpCF3,1Nt]; n = 2, [TpCF3,2Nt]) show essentially equal binding pockets. The surprising differences in the electron density on the CuI ions must therefore be the result of different conformations of the 1- and 2-naphthyl groups.

    2. EPR of Scorpionates

      The Original CoII Heteroscorpion­ates Revisited: On the EPR of Pseudotetrahedral CoII

      Robert R. Baum, William K. Myers, Samuel M. Greer, Robert M. Breece and David L. Tierney

      Version of Record online: 2 MAR 2016 | DOI: 10.1002/ejic.201501356

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      Solution spectroscopy of a series of five (RBpx)2Co complexes is reported. A frozen solution EPR study shows that all of the complexes have MS = 3/2 ground states, and offer insight into the complex EPR of pseudotetrahedral CoII.

    3. Tripodal Ligands

      FeII and CoII Complexes with Click-Derived Tripodal Ligands: Influence of the Peripheral Substituents on Geometric Structures and Magnetic Properties

      David Schweinfurth, Serhiy Demeshko, Michael G. Sommer, Sebastian Dechert, Franc Meyer and Biprajit Sarkar

      Version of Record online: 1 MAR 2016 | DOI: 10.1002/ejic.201501385

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      In FeII and CoII complexes with click-derived tripodal ligands, the geometric structures around the metal centers, as well as their spin states are shown to be dictated by the peripheral substituents (phenyl vs. benzyl) on the tripodal ligands.

    4. Silicon Scorpionates

      The First Structurally Characterised Example of Silicon in an S6 Coordination Sphere

      Annemarie Marckwordt, Rajeev Rajasekharan-Nair, Graham Steel, Alan R. Kennedy, John Reglinski and Mark D. Spicer

      Version of Record online: 1 MAR 2016 | DOI: 10.1002/ejic.201501269

      Thumbnail image of graphical abstract

      Reaction of NaTmPh with SiI4 results in an octahedral Silicon complex in an S6 ligand environment. The resulting compound has been characterised crystallographically and been the subject of DFT calculations.

    5. Nickel(II) Borohydrides

      Variable Borohydride Hapticity in Nickel(II) Scorpionate Complexes [(TpR,Me)Ni(ηn-BH4)]: TpR,Me = hydro­tris­{3-R-5-methyl-1-pyrazolyl}­borate; R = Ph, n = 3 vs. R = Me, n = 4

      Colin P. Kruse, Tapash Deb, Ahmed M. Aboelenen, Caitlin M. Anderson, Jeffrey L. Petersen and Michael P. Jensen

      Version of Record online: 24 FEB 2016 | DOI: 10.1002/ejic.201501330

      Thumbnail image of graphical abstract

      [(TpPh,Me)Ni(BH4)] exhibits η3-BH4 coordination with two bridging and two terminal hydrides on boron. This contrasts with [(TpMe,Me)Ni(BH4)], previously shown to have an η4-BH4 ligand. The borohydride hapticities diverge as a result of the different 3-pyrazole substituents on the scorpionate co-ligands, and can be distinguished by FTIR spectroscopy.

    6. Be Scorpionate Complexes

      On the Stability of Trimeric Beryllium Hydroxide Scorpionate Complexes

      Dominik Naglav, Briac Tobey, Christoph Wölper, Dieter Bläser, Georg Jansen and Stephan Schulz

      Version of Record online: 22 FEB 2016 | DOI: 10.1002/ejic.201501433

      Thumbnail image of graphical abstract

      Two trimeric beryllium hydroxide scorpionate complexes [Be3(µ-OX)3(Tp)3] (X = H: 1, D: 2) and [BeBr3(µ-OH)3(Br)3(thf)6] were structurally characterized. The six-membered Be3O3 ring of 1 is stable in both solution and the gas phase as was shown by temperature-dependent 1H and 9Be NMR spectroscopy and theoretical calculations.

  35. Microreviews

    1. Dinitrogen Complexes

      Scorpionates of the “Tetrahedral Enforcer” Variety as Ancillary Ligands for Dinitrogen Complexes of First Row Transition Metals (Cr–Co)

      Daniel C. Cummins, Glenn P. A. Yap and Klaus H. Theopold

      Version of Record online: 18 FEB 2016 | DOI: 10.1002/ejic.201501326

      Thumbnail image of graphical abstract

      Dinitrogen complexes of the first row transition metals Cr–Co supported by tris(pyrazolyl)borate ligands have been prepared and structurally characterized. Their role as precursors for O2 activation reactions is summarized.

  36. Full Papers

    1. Polymerization of Norbornene

      Switchable Polymerization of Norbornene Derivatives by a Ferrocene-Palladium(II) Heteroscorpionate Complex

      Mark Abubekerov, Scott M. Shepard and Paula L. Diaconescu

      Version of Record online: 12 FEB 2016 | DOI: 10.1002/ejic.201501295

      Thumbnail image of graphical abstract

      A cationic ferrocene-chelating heteroscorpionate methylpalladium complex catalyzes the addition polymerization of norbornene and norbornene derivatives. Redox switchable polymerization of these monomers was also accomplished.

  37. Microreviews

    1. C–H Activation

      Transition Metal Mediated C–H Activation and Functionalization: The Role of Poly(pyrazolyl)borate and Poly(pyrazolyl)alkane Ligands

      Bradley A. McKeown, John P. Lee, Jiajun Mei, Thomas R. Cundari and T. Brent Gunnoe

      Version of Record online: 12 FEB 2016 | DOI: 10.1002/ejic.201501470

      Thumbnail image of graphical abstract

      This microreview presents work surrounding the development and study of Tp-supported platinum group metal complexes for stoichiometric and catalytic C–H bond activation. From κ2- and κ3-coordination modes to increased sterics to electronic parameters, Tp and related ligands have played an important role in the observed reactivity of Ru, Rh and Pt-mediated C–H bond activation reactions.

  38. Full Papers

    1. Fluorinated Scorpionates

      Mixed Alkyl-Perfluoroalkyl Silver Scorpionates: Synthesis, X-ray Structures and Stabilizing Substituent Effects

      Andrei Loas and Sergiu M. Gorun

      Version of Record online: 12 FEB 2016 | DOI: 10.1002/ejic.201501450

      Thumbnail image of graphical abstract

      Seven new mixed alkyl-perfluoroalkyl silver tris(pyrazolyl)borate complexes are reported and structurally characterized. Single-crystal X-ray analysis defines a structural model that predicts interatomic distances and rationalizes the relative stability of members of this class of compounds.

  39. Communications

    1. Fluorinated Scorpionates

      Isolable Ethylene Complexes of Copper(I), Silver(I), and Gold(I) Supported by Fluorinated Scorpionates [HB{3-(CF3),5-(CH3)Pz}3] and [HB{3-(CF3),5-(Ph)Pz}3]

      Shawn G. Ridlen, Jiang Wu, Naveen V. Kulkarni and H. V. Rasika Dias

      Version of Record online: 9 FEB 2016 | DOI: 10.1002/ejic.201501365

      Thumbnail image of graphical abstract

      Partially fluorinated scorpionate [HB{3-(CF3),5-(CH3)Pz}3] allows the stabilization of molecules with gold(I), silver(I) and copper(I) ethylene adducts. Related adducts supported by [HB{3-(CF3),5-(CH3)Pz}3] are also included for comparisons. Notable differences exist in scorpionate modes of coordination and ethylene carbon chemical shift values.

  40. Microreviews

    1. Hydroelementation

      Hydroelementation of Unsaturated C–C Bonds Catalyzed by Metal Scorpionate Complexes

      Matthew Wathier and Jennifer A. Love

      Version of Record online: 5 FEB 2016 | DOI: 10.1002/ejic.201501272

      Thumbnail image of graphical abstract

      A review of recent advances in hydroelementation (E = S, N, O, P) of alkenes and alkynes catalyzed by metal complexes bearing scorpionate-type ligands.

  41. Communications

    1. Agostic Interactions

      Enhancing Reactivity of Directly ­Observable B–H–Pt Interactions through Conformational Rigidity

      Shrinwantu Pal, Marcus W. Drover, Brian O. Patrick and Jennifer A. Love

      Version of Record online: 3 FEB 2016 | DOI: 10.1002/ejic.201501305

      Thumbnail image of graphical abstract

      Trimethylplatinum(IV) complexes featuring agostic B–H–Pt interactions supported by bis(pyrazolyl)borate (Bp) and bis(3,5-dimethylpyrazolyl)borate (Bp*) ligands show interesting structural differences both in solution and the solid state. These differences result in enhanced reactivity of the Bp* complexes towards hydroboration of acetonitrile and protonolysis with methanol.

  42. Full Papers

    1. OLEDs

      Two Green-Phosphorescent Iridium Complexes with 2-Phenylpyrimidine Derivatives and Tetraphenylimido­diphosphinate for Efficient Organic Light-Emitting Diodes

      Song Zhang, Jing-Cheng Xia, Zheng-Guang Wu, Guang-Zhao Lu, Yue Zhao and You-Xuan Zheng

      Version of Record online: 2 FEB 2016 | DOI: 10.1002/ejic.201501318

      Thumbnail image of graphical abstract

      Organic light-emitting diodes (OLEDs) based on IrIII complexes containing pyrimidine derivatives as cyclometalated ligands and tetraphenylimidodiphosphinate as ancillary ligand exhibited maximum current efficiencies as high as 81.91 and 71.17 cd A–1 and maximum external quantum efficiencies of 20.8 and 21.3 %, respectively, with low-efficiency roll-off.

  43. Microreviews

    1. Metallacycles

      Bis(pyrazol-1-yl)(pyridin-x-yl)methane Ligands – Mono- or Ditopic Ligands in Complexes and Supramolecular Frameworks

      Blanca R. Manzano, Félix A. Jalón, M. Carmen Carrión and Gema Durá

      Version of Record online: 1 FEB 2016 | DOI: 10.1002/ejic.201501271

      Thumbnail image of graphical abstract

      Bis(pyrazol-1-yl)(pyridin-x-yl)methane ligands give rise to a rich variety of complexes and supramolecular frameworks with a wide range of transition metals. With x = 2, the ligands behave as monotopic, usually with tripodal coordination, whereas with x = 3 or 4 they act as bridges, giving rise to polymers or dinuclear or trinuclear discrete species.

  44. Full Papers

    1. Iron Scorpionate Complexes

      Mononuclear Iron-(hydro/semi)­quinonate Complexes Featuring Neutral and Charged Scorpionates: Synthetic Models of Intermediates in the Hydroquinone Dioxygenase Mechanism

      Amanda E. Baum, Sergey V. Lindeman and Adam T. Fiedler

      Version of Record online: 29 JAN 2016 | DOI: 10.1002/ejic.201501380

      Thumbnail image of graphical abstract

      Both neutral and anionic scorpionates are used to prepare synthetic models of hydroquinone dioxygenases (HQDOs) – a class of mononuclear nonheme enzymes. The different ligands mimic variations in coordination geometry within the HQDO family. The ferric-hydroquinonate complexes undergo reversible deprotonation to yield ferrous-semiquinonate species.

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