European Journal of Inorganic Chemistry

Cover image for Vol. 2014 Issue 25

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

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.965

ISI Journal Citation Reports © Ranking: 2013: 10/44 (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

  1. Full Papers

    1. Ligand Design

      Aminoalkyl-1,1-bis(phosphinic acids): Stability, Acid–Base, and Coordination Properties

      Tomáš David, Soňa Procházková, Jan Kotek, Vojtěch Kubíček, Petr Hermann and Ivan Lukeš

      Article first published online: 30 JUL 2014 | DOI: 10.1002/ejic.201402420

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      Four geminal bisphosphinates were synthesized, and their acid–base properties and coordination behaviour with Cu2+, Zn2+ and Ni2+ ions were studied. The compounds show lower amine basicity and complex stability constants than those of analogous bisphosphonates. In the solid-state structures of the Ca2+ and Cu2+ complexes, the bisphosphinates are coordinated in O,O′-chelating mode.

    2. Iron Phosphonate

      A Direct Three-Component Reaction for the Isolation of a Nonanuclear Iron(III) Phosphonate

      Joydeb Goura, Junjie Liu, Paul Goddard and Vadapalli Chandrasekhar

      Article first published online: 30 JUL 2014 | DOI: 10.1002/ejic.201402371

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      The reaction of anhydrous ferric chloride with cyclopentylphosphonic acid and pivalic acid in the presence of triethylamine at room temperature afforded a nonanuclear iron(III) phosphonate. It possesses a cage structure with a distorted icosahedral core. Mössbauer studies confirm high-spin FeIII, whereas magnetic measurements suggest strong antiferromagnetic couplings between the Fe3+ ions.

    3. Magnetic Properties

      Electronic and Magnetic Properties of a Gadolinium(III) Schiff Base Complex

      Apoorva Upadhyay, Chinmoy Das, Muralidharan Shanmugam, Stuart K. Langley, Keith S. Murray and Maheswaran Shanmugam

      Article first published online: 30 JUL 2014 | DOI: 10.1002/ejic.201402219

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      A monomeric GdIII Schiff base complex was isolated and its electronic and magnetic properties were investigated in detail. From variable-temperature X-band dilution studies, we conclude that magnetic anisotropy arises in this complex due to low symmetry around GdIII provided by the ligand field.

    4. Silver Clusters

      Synthesis of Atomically Precise Silver Clusters by Using the Miscibility Principle

      Atanu Ghosh and Thalappil Pradeep

      Article first published online: 28 JUL 2014 | DOI: 10.1002/ejic.201402587

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      Silver and gold clusters have been synthesized by using the miscibility principle of solvents. Three solvents, that is, water, methanol, and toluene (or chloroform) have been used to synthesize different silver clusters by this method without phase-transfer agents. Separate regions of the phase diagram (a, b, c, and d) produce distinctly different clusters from the same reactant compositions.

    5. Blue Emitters

      Synthesis, Structure, and Photophysical Properties of Blue-Emitting Zinc(II) Complexes with 3-Aryl-Substituted 1-Pyridylimidazo[1,5-a]pyridine Ligands

      G. Attilio Ardizzoia, Stefano Brenna, Sara Durini, Bruno Therrien and Mattia Veronelli

      Article first published online: 28 JUL 2014 | DOI: 10.1002/ejic.201402415

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      Zinc(II) complexes containing N,N-bidentate 3-aryl-substituted 1-pyridylimidazo[1,5-a]pyridine ligands show blue emission in the solid state with absolute photoluminescent quantum yields (ΦPL) of up to 0.40. The different emission properties of the complexes are related to the presence of intermolecular O–H···N hydrogen bonds.

    6. Lewis Acids

      Poly-Boron, -Silicon, and -Gallium Lewis Acids by Hydrometallation of 1,5- and 1,8-Dialkynylanthracenes

      Jan-Hendrik Lamm, Jan Horstmann, Jan H. Nissen, Jan-Henrik Weddeling, Beate Neumann, Hans-Georg Stammler and Norbert W. Mitzel

      Article first published online: 25 JUL 2014 | DOI: 10.1002/ejic.201402376

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      A series of B-, Si- and Ga-containing poly-Lewis acids were synthesised by converting 1,5- and 1,8-dialkynylanthracene derivatives in hydrometallation reactions. Some of the compounds reacted with diethyl ether, which demonstrates the variable behaviour of the Lewis acidic compounds towards Lewis basic molecules.

    7. Bridged Complexes

      Synthesis of Trinuclear Heterobimetallic Cyanido-Bridged Complexes from the Reaction of [MnI(CN)(CO)(tBuNC)4] with Transition-Metal Chlorides

      Kathi Carl, Anke Sterzik, Helmar Görls and Wolfgang Imhof

      Article first published online: 24 JUL 2014 | DOI: 10.1002/ejic.201402398

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      The reaction of [Mn(CN)(CO)(tBuNC)4] with transition-metal chlorides led to the formation of cyanide-bridged trinuclear coordination compounds. If CuII or FeII was used as the central metal atom, intramolecular electron transfer (M = Cu, Fe) and disproportionation processes (M = Fe) were observed and investigated by UV/Vis and EPR spectroscopy and X-ray crystallography.

    8. Cluster Compounds

      Coordination Cluster Analogues of the High-Spin [Mn19] System with Functionalized 2,6-Bis(hydroxymethyl)phenol Ligands

      Samir Mameri, Ayuk M. Ako, Fatma Yesil, Marcel Hibert, Yanhua Lan, Christopher E. Anson and Annie K. Powell

      Article first published online: 24 JUL 2014 | DOI: 10.1002/ejic.201402327

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      The robustness of the inorganic {MnIII12MnII74-O)8} core of Mn19 systems with variously functionalized encapsulating ligands is demonstrated by the invariance of the record S = 83/2 spin state. Chemical modification aimed towards attaching the molecule to various substrates does not interfere with the electronic structure.

    9. Solar Cells

      Optimal-Temperature-Based Highly Efficient NiS Counter Electrode for Quantum-Dot-Sensitized Solar Cells

      Hee-Je Kim, Tae-Bin Yeo, Soo-Kyoung Kim, S. Srinivasa Rao, A. Dennyson Savariraj, K. Prabakar and Chandu V. V. M. Gopi

      Article first published online: 24 JUL 2014 | DOI: 10.1002/ejic.201402026

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      In quantum-dot-sensitized solar cells, nickel sulfide is a highly efficient catalyst by reducing the redox species that mediate the reduction of the sensitizer after electron injection. The catalytic activity of the NiS counter electrode depends on the deposition temperature. This is supported by cyclic voltammetry, electrochemical impedance spectroscopy (EIS), and Tafel polarization measurements.

    10. Nanostructures

      Photoinduced Topological Transformation in Mesoscopic Inorganic Nanoparticles: Application as a UV Sensor

      Santu Das, Preethi Thomas and Soumyajit Roy

      Article first published online: 22 JUL 2014 | DOI: 10.1002/ejic.201402297

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      Irradiation of ammonium heptamolybdate tetrahydrate soft-oxometalate (SOM) nanorods with UV light leads to their topological transformation into molybdenum blue SOM nanospheres. This transformation is accompanied by a colour change from colourless to blue, which can be exploited for UV sensing. Thus, when a particular threshold amount of UV irradiation is absorbed, the nanorods change colour.

    11. Copper Catalysts

      Polynuclear Copper(II) Complexes as Catalysts for the Peroxidative Oxidation of Cyclohexane in a Room-Temperature Ionic Liquid

      Raja Jlassi, Ana P. C. Ribeiro, M. Fátima C. Guedes da Silva, Kamran T. Mahmudov, Maximilian N. Kopylovich, Tatiana B. Anisimova, Houcine Naïli, Gonçalo A. O. Tiago and Armando J. L. Pombeiro

      Article first published online: 21 JUL 2014 | DOI: 10.1002/ejic.201402352

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      Multinuclear CuII complexes with a catalytic metal centre and an acid functionality catalyze the peroxidative oxidation of cyclohexane in acid-free water/air/CH3CN or ionic liquid media.

  2. Microreviews

    1. Silver(I) Cyanoximates

      Synthesis, Properties, and Applications of Light-Insensitive Silver(I) Cyanoximates

      Nikolay Gerasimchuk

      Article first published online: 18 JUL 2014 | DOI: 10.1002/ejic.201402251

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      Twelve coordination polymers of silver(I) cyanoximates of composition AgL were found to be very stable towards visible light. Three areas of potential practical relevance of these unusual complexes have emerged. The chemical, structural, technological, and biological aspects of the applications of these compounds are reviewed.

    2. Heterometallic Complexes

      Polynuclear Heterometallic Complexes from Metal Powders: The “Direct Synthesis” Approach

      Dmytro S. Nesterov, Oksana V. Nesterova, Vladimir N. Kokozay and Armando J. L. Pombeiro

      Article first published online: 18 JUL 2014 | DOI: 10.1002/ejic.201402266

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      In this review we summarize our experience in the field of the “direct synthesis” of polynuclear heterometallic complexes, covering preparative and structural aspects as well as applications of the compounds obtained.

    3. Stimuli-Responsive Materials

      Stimuli-Responsive Dynamic Gold Complexes

      Csaba Jobbágy and Andrea Deák

      Article first published online: 10 JUL 2014 | DOI: 10.1002/ejic.201402249

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      A general overview on stimuli-responsive gold(I) and gold–heterometal derivatives is presented with a special focus on the impact of noncovalent interactions on molecular structures, packing patterns and solid-state properties. Representative examples with thermo-, mechano- and vapochromic luminescence, vapochromism and gas sorption properties have been selected.

  3. Short Communications

    1. Electron-Transfer Reactions

      Electron-Transfer Rate Enhancements in Nanosized Waterpools

      Bret B. Lorenz, Debbie C. Crans and Michael D. Johnson

      Article first published online: 9 JUL 2014 | DOI: 10.1002/ejic.201402307

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      The kinetics of electron-transfer reactions between metal complexes and ascorbic acid (vitamin C) are reported in both aqueous media and in nanosized water droplets formed in microemulsions. Rate-constant enhancements of up to two orders of magnitude are reported.

  4. Full Papers

    1. Selective Crystallization

      Sulfonated Polymethylsiloxane as an Additive for Selective Calcium Oxalate Crystallization

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

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

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

    2. Pincer Ligand Complexes

      Synthesis and Redox Properties of PNP Pincer Complexes Based on N-Methyl-4,4′-bipyridinium

      Yoshihiro Miyake, Kazunari Nakajima, Yu Higuchi and Yoshiaki Nishibayashi

      Article first published online: 26 JUN 2014 | DOI: 10.1002/ejic.201402349

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      We have designed and prepared a series of novel PNP pincer ligands based on N-methyl-4,4′-bipyridinium for the construction of stable complexes toward two steps of single electron transfer reactions, where p-quinoid-type complexes play a key role. The rhodium complex bearing PNP pincer ligand based on N-methyl-4,4′-bipyridinium is also found to work as a catalyst for dihydrogen production under the photoinduced electron-transfer conditions.

    3. Macroions

      Self-Assembly of Subnanometer-Scaled Polyhedral Oligomeric Silsesquioxane (POSS) Macroions in Dilute Solution

      Jing Zhou, Panchao Yin, Lang Hu, Fadi Haso and Tianbo Liu

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402237

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      Two oppositely charged polyhedral oligomeric silsesquioxane (POSS) macroions with identical charge and similar sizes can self-assemble into blackberry-type supramolecular structures in dilute solution. This transition from simple macroions to assemblies can be regulated by the solvent polarity.

    4. Nickel Hydride Electrocatalysts

      A NiII–Bis(diphosphine)–Hydride Complex Containing Proton Relays – Structural Characterization and Electrocatalytic Studies

      Parthapratim Das, Ryan M. Stolley, Edwin F. van der Eide and Monte L. Helm

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402250

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      A new member of the [Ni(PR2NR′2)2]2+ family of electrocatalysts is reported. Complex [Ni(PiPr2NPh2)2]2+ is an electrocatalyst for proton reduction to form H2. Additionally, we have isolated and structurally characterized the NiII–hydride [HNi(PiPr2NPh2)2]+.

  5. Microreviews

    1. Dinuclear Technetium Complexes

      A Decade of Dinuclear Technetium Complexes with Multiple Metal–Metal Bonds

      Frederic Poineau, Paul M. Forster, Tanya K. Todorova, Erik V. Johnstone, William M. Kerlin, Laura Gagliardi, Kenneth R. Czerwinski and Alfred P. Sattelberger

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402340

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      This review covers the metal–metal bond chemistry of dinuclear technetium complexes published in the period 2005–2014. The preparation, solid-state and electronic structures, and spectroscopic properties of (nBu4N)2Tc2X8, Tc2(O2CCH3)4X2, Tc2(O2CCH3)2Cl4, cesium salts of Tc2X83–, and Tc2X4(PMe3)4 (X = Cl, Br) are presented.