European Journal of Inorganic Chemistry

Cover image for Vol. 2015 Issue 21

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: 8/44 (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

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  1. 1 - 63
  1. Full Papers

    1. Macrocyclic Ligands

      Copper(II) Cyclam Complexes with N-­Propionic Acid Pendant Arms

      Manja Kubeil, Kristof Zarschler, Jens Pietzsch, Werner Kraus, Peter Comba and Holger Stephan

      Article first published online: 27 JUL 2015 | DOI: 10.1002/ejic.201500510

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      Four cyclam ligands with different numbers of N-propionic acid pendant arms were screened as potential bifunctional chelators for CuII radioisotopes. The pendant arms of the ligands strongly influence the stability of the CuII complexes formed. In this series, the cyclam ligands with one (HL1) and two N-propionic acid arms (H2L2) are promising ligands for radiopharmaceutical applications.

    2. Metal–Organic Frameworks

      Experimental and Theoretical Investigations of CO2 Sorption by a 3D In-MOF with Multiple 1D Channels

      Ja-Min Gu, Jin-Yeon Hong, Yong Sun Won, Sung Soo Park and Seong Huh

      Article first published online: 24 JUL 2015 | DOI: 10.1002/ejic.201500394

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      The low-pressure CO2 sorption capacity of the 3D In-MOF (Et2NH2)[In(2,6-NDC)2]·2H2O·DEF (I) (where 2,6-NDC is 2,6-naphthalenedicarboxylate and DEF is N,N-diethylformamide) was investigated at various temperatures.

    3. Oxygen Atom Transfer

      Mechanisms of Oxygen Atom Transfer between Main-Group Elements

      Jeanet Conradie, Steffen Berg and Abhik Ghosh

      Article first published online: 24 JUL 2015 | DOI: 10.1002/ejic.201500591

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      In the major quantum chemical study of oxygen atom transfer between main-group element centers, DFT calculations unequivocally indicate a one-step, SN2-like pathway as the normative mechanism, as opposed to a two-step associative-dissociative sequence that is common for transition metals.

    4. Nanoparticle-Modified Ferritins

      Orthogonal Functionalization of Ferritin via Supramolecular Re-Assembly

      Silvia J. Spa, Anton Bunschoten, Marcus T. M. Rood, Ruud J. B. Peters, Abraham J. Koster and Fijs W. B. van Leeuwen

      Article first published online: 24 JUL 2015 | DOI: 10.1002/ejic.201500386

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      To investigate the control on ferritin functionalization by supramolecular re-assembly, ferritin with modular functionality and still capable of iron mineralization was created. The ratio in which Cy3-, Cy5-, and non-functionalized subunits were mixed, was indicative for the ratio in which the variable subunits were observed in the re-assembled capsids.

    5. Group 13 Element Complexes

      Synthesis and Characterization of GaIII, InIII and LuIII Complexes of a Set of dtpa Bis-Amide Ligands

      Julia Greiser, Tino Hagemann, Tobias Niksch, Philipp Traber, Stephan Kupfer, Stefanie Gräfe, Helmar Görls, Wolfgang Weigand and Martin Freesmeyer

      Article first published online: 23 JUL 2015 | DOI: 10.1002/ejic.201500436

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      The synthesis and characterization of new GaIII, InIII and LuIII complexes of five dtpa bis-amides are described. As determined by single-crystal structure analysis, the InIII complexes are hepta- or octa-coordinated, whereas the LuIII are nona-coordinated in the solid state. NMR studies were undertaken to characterize the coordination behaviour of the complexes in solution.

    6. Fluorescent Quantum-Dot Bioconjugates

      Cytocompatible Fluorescent Quantum Dot/PEG-Chitosan Bioconjugates for Nanomedicine Applications

      Alexandra A. P. Mansur, Camila G. de Almeida, Sandhra M. de Carvalho, Lucas V. de Faria, Mauro V. de Almeida and Herman S. Mansur

      Article first published online: 23 JUL 2015 | DOI: 10.1002/ejic.201500441

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      Novel nanobioconjugates based on Cd-based quantum dots and a PEGylated chitosan derivative as capping ligand have been designed and synthesised by a single-step aqueous route at room temperature. These nanohybrids are luminescent and cytocompatible towards two cell lines tested in vitro, therefore showing potential as biomarkers in nanomedicine applications.

    7. Prochiral Sulfides

      Recognition of Prochiral Sulfides in Five-Coordinate PtII Complexes

      Luisa Calvanese, Maria E. Cucciolito, Angela D'Amora, Gabriella D'Auria, Antonio Esposito, Roberto Esposito, Lucia Falcigno and Francesco Ruffo

      Article first published online: 23 JUL 2015 | DOI: 10.1002/ejic.201500523

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      A stereochemical study on five-coordinate complexes of PtII containing a prochiral alkene (E-R1O2CCH=CHCO2R1) and a prochiral sulfide R2SR3, of general formula [PtMe(R2SR3)(dmphen) (E-R1O2CCH=CHCO2R1)]BF4, has been described. It has been demonstrated that there is mutual recognition between the prochiral ligands in the presence of aryl sulfides R2SAr, whose origin has also been explained.

    8. Nanostructure Precursors

      One-Pot Synthesis of an Oxalato-Bridged CuII Coordination Polymer Containing an In Situ Produced Pyrazole Moiety: A Precursor for the Preparation of CuO Nano­structures

      Samira Bahemmat, Bernhard Neumüller and Mitra Ghassemzadeh

      Article first published online: 23 JUL 2015 | DOI: 10.1002/ejic.201500255

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      The one-pot reaction of acetylacetone, thiosemicarbazide, oxalic acid and copper(II) chloride in a molar ratio of 2:2:1:2 affords coordination polymer [Cu2(C2O4)(L)2Cl2(MeOH)2]n (1) (L = 3,5-dimethyl-1H-pyrazole generated in situ). Thermolysis of complex 1 under neat conditions in air at 550 °C and 1000 °C generates CuO nanoparticles and nanosheets, respectively.

    9. Light-Activated Prodrugs

      Towards Selective Light-Activated RuII-Based Prodrug Candidates

      Cristina Mari, Vanessa Pierroz, Anna Leonidova, Stefano Ferrari and Gilles Gasser

      Article first published online: 22 JUL 2015 | DOI: 10.1002/ejic.201500602

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      Three novel RuII–polypyridyls have been synthesized and derivatized with a photolabile protecting group and two peptides. The targeting moieties allow a higher uptake in cancer cells compared with normal cells. The release of the metal component upon irradiation provided complete control of the cytotoxicity with a mechanism of action that is independent of the presence of oxygen in the tissues.

    10. Dioxygen Activation

      Dioxygen Activation by an in situ Reduced CuII Hydrazone Complex

      Christian Radunsky, Jutta Kösters, Matthias C. Letzel, Sivathmeehan Yogendra, Christian Schwickert, Sinja Manck, Biprajit Sarkar, Rainer Pöttgen, Jan J. Weigand, Johannes Neugebauer and Jens Müller

      Article first published online: 20 JUL 2015 | DOI: 10.1002/ejic.201500556

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      A CuII complex of a hydrazone ligand with N,N,S-donor functionality is reported that, after in situ reduction, is able to activate dioxygen, leading to a hydroxylation of the ligand and finally resulting in the formation of a CuII complex of a hydrazone ligand acting as an N,N,O-donor.

    11. Ionic Liquids

      Easily Vaporizable Ionic Liquids – No Contradiction!

      Martin Köckerling, Tim Peppel, Philipp Thiele, Sergey P. Verevkin, Vladimir N. Emel'yanenko, Artemiy A. Samarov and Wolfgang Ruth

      Article first published online: 20 JUL 2015 | DOI: 10.1002/ejic.201500391

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      Ionic liquids (ILs) are commonly known as compounds with negligible vapour pressure, which makes them difficult to boil/distil or sublime. Surprisingly, ILs with imidazolium-based cations with the specialty of N-bonded silylorganic groups sublime very easily. The process of sublimation has been investigated thoroughly with physicochemical methods and theoretical calculations.

    12. Polyoxomolybdate Oxidation

      Selective Oxidation of Sulfides Catalyzed by the Nanocluster Polyoxomolybdate (NH4)12[Mo36(NO)4O108(H2O)16]

      Mojtaba Amini, Hadi Naslhajian, S. Morteza F. Farnia and Małgorzata Hołyńska

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500528

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      A polyoxomolybdate, (NH4)12[Mo36(NO)4O108(H2O)16]·30.84H2O ({Mo36}), has been synthesized and successfully used in the oxidation of sulfides with urea hydrogen peroxide as oxidant.

    13. Low-Coordinate Phosphorus

      π-Excess σ2P=C–N–Heterocycles: Catalytic P-Arylation and Alkylation of N-Alkyl-1,3-benzazaphospholes and Isolation of P,N-Disubstituted Dihydrobenzaza­phosphole P-Oxides

      Basit Niaz, Bhaskar R. Aluri, Peter G. Jones and Joachim W. Heinicke

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500532

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      Aromatic σ2P-heterocycles are unreactive to aryl/alkyl halides. Heating in the presence of Pd or Pt catalysts and a suitable base, however, allows direct P-arylation or P-alkylation. The intermediate products are extremely moisture-sensitive and are transformed into phosphine oxides. Et3OBF4 provides benzazaphospholium salts without a catalyst, but these also tend to hydrolyze to phosphine oxides.

    14. Pd Thiosemicarbazone Catalysts

      Water-Soluble Palladium(II) Sulfonated Thiosemicarbazone Complexes: Facile Synthesis and Preliminary Catalytic Studies in the Suzuki–Miyaura Cross-Coupling Reaction in Water

      Leah C. Matsinha, Jincheng Mao, Selwyn F. Mapolie and Gregory S. Smith

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500588

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      Mono- and binuclear thiosemicarbazone complexes were synthesized and characterized. The mononuclear complexes are very stable in water and all the catalysts are active for the Suzuki–Miyaura cross-coupling reaction of various substrates. The mononuclear catalysts were more active than their binuclear analogues. Catalyst 4 could be recycled efficiently twice.

  2. Correspondence

    1. Sensors for Iron Ions

      Key Considerations for Sensing FeII and FeIII in Aqueous Media

      Shawn C. Burdette

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500566

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      Recently, Ghosh et al. reported on the fluorescent response of N-(2-aminoethyl)naphthalen-1-amine toward FeII, FeIII, and HgII (K. Ghosh, S. Rathi, P. Gupta, P. Vashisth, V. Pruthi, Eur. J. Inorg. Chem. 2015, 311), concluding that metal binding to the diamine chelator leads to chelation-induced quenching; however, the experimental protocols are incompatible with the aqueous chemistry of FeIII.

  3. Full Papers

    1. Cu Oxidation Catalysts

      Trinuclear CuII Structural Isomers: Coordination, Magnetism, Electrochemistry and Catalytic Activity towards the Oxidation of Alkanes

      Manas Sutradhar, Luísa M. D. R. S. Martins, M. Fátima C. Guedes da Silva, Kamran T. Mahmudov, Cai-Ming Liu and Armando J. L. Pombeiro

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500440

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      Three isomeric CuII complexes derived from Schiff base (3,5-di-tert-butyl-2-hydroxybenzylidene)-2-hydroxybenzohydrazide and three different CuII sources are reported. Their structural, electrochemical and magnetic properties as well as catalytic activity toward the peroxidative oxidation of cyclohexane to cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone under mild conditions are described.

    2. HNO Reactivity of Vitamin B12

      Studies on the Reaction of Reduced Vitamin B12 Derivatives with the Nitrosyl ­Hydride (HNO) Donor Angeli's Salt: HNO Oxidizes the Transition-Metal Center of Cob(I)alamin

      Harishchandra Subedi and Nicola E. Brasch

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500442

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      Kinetic studies on the reaction between cob(II)alamin [Cbl(II)] and Angeli's salt (AS) show that AS decomposition to give HNO is the rate-determining step. A mechanism is proposed involving a cob(I)alamin [Cbl(I)] intermediate that is oxidized back to Cbl(II) by a second HNO molecule. Separate studies on the reaction of Cbl(I) with AS support this mechanism.

    3. Ru Metal-Organic Frameworks

      Controlled SBU Approaches to Isoreticular Metal-Organic Framework Ruthenium-Analogues of HKUST-1

      Wenhua Zhang, Olesia Kozachuk, Raghavender Medishetty, Andreas Schneemann, Ralph Wagner, Kira Khaletskaya, Konstantin Epp and Roland A. Fischer

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500478

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      A controlled secondary building unit approach (CSA) was employed to obtain a series of isostructural ruthenium metal-organic frameworks (MOFs) of the general formula [Ru3(BTC)2Xx]·Gg (BTC = 1,3,5-benzenetricarboxylate; X = counter anion, G = guest molecules) which are analogues of [Cu3(BTC)2] (HKUST-1).

    4. Water Oxidation Catalysts

      Mechanisms and Factors Controlling Photoisomerization Equilibria, Ligand Exchange, and Water Oxidation Catalysis Capabilities of Mononuclear Ruthen­ium(II) Complexes

      Masanari Hirahara, Tomoya Hakamata, Aaron B. League, Mehmed Z. Ertem, Kosuke Takahashi, Sho Nagai, Keisuke Inaba, Hirosato Yamazaki, Kenji Saito, Tatsuto Yui, Christopher J. Cramer and Masayuki Yagi

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500642

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      The photoisomerization equilibrium between distal- and proximal-[Ru(tpy)(pyqu)OH2]2+ [d- and p-RuH2O, tpy = 2,2′,6′,2″-terpyridine, pyqu = 2-(2-pyridyl)quinoline] is illustrated. Isolation of distal- and proximal-[Ru(tpy)(pyqu)Cl]+ and d- and p-RuH2O isomers enabled comprehensive studies on geometric structures, ligand exchange and redox reactions, and water oxidation catalysis for these isomers.

  4. Short Communications

    1. Silica Hybrids

      Biomimetic Autocatalytic Synthesis of Organized Silica Hybrids

      Erol Licsandru, Eddy Petit, Simona Moldovan, Ovidiu Ersen and Mihail Barboiu

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500701

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      Biomimetic formation of self-organized silica hybrids can be achieved by self-catalytic processes. Active imidazole moieties catalyze hydrolysis/condensation reactions in the absence of conventional sol–gel catalysts. Siloxane–imidazole proxy interactions are beneficial for the synthesis. As in natural systems, highly organized hybrid silica can be obtained with a very high degree of control.

  5. Full Papers

    1. Metal-Encapsulated MOFs

      Pd@UiO-66-Type MOFs Prepared by Chemical Vapor Infiltration as Shape-Selective Hydrogenation Catalysts

      Ignacio Luz, Christoph Rösler, Konstantin Epp, Francesc X. Llabrés i Xamena and Roland A. Fischer

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500299

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      Encapsulation of Pd nanoparticles inside the pores of UiO-66 and UiO-67 by chemical vapor infiltration leads to shape-selective catalysts, as shown for the hydrogenation of carbonyl compounds of different steric hindrance.

    2. Cytotoxic Copper Complexes

      Structural, Magnetic, DFT, and Biological Studies of Mononuclear and Dinuclear CuII Complexes with Bidentate N-Heteroaromatic Schiff Base Ligands

      Tamara Todorović, Sonja Grubišić, Matej Pregelj, Marko Jagodič, Sonja Misirlić-Denčić, Marija Dulović, Ivanka Marković, Olivera Klisurić, Aleksandar Malešević, Dragana Mitić, Katarina Anđelković and Nenad Filipović

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500349

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      We report the synthesis and XRD structures of monomeric and dimeric CuII complexes 1 and 2. The magnetic properties of 1, 2, and three similar CuII complexes are discussed on the basis of electron paramagnetic resonance (EPR) spectroscopy studies combined with DFT calculations. The antitumor action of the CuII complexes against six different cancer cell lines is investigated.

    3. Large Bite Angle P Ligands

      Mononuclear, Tetranuclear and 1D Polymeric Copper(I) Complexes of Large Bite Bisphosphines Containing Nitrogen and Oxygen Donor Atoms

      Sajad A. Bhat, Joel T. Mague and Maravanji S. Balakrishna

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500418

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      This paper describes the synthesis of new bisphosphines containing nitrogen and oxygen donor atoms, N,N-bis(diphenylphosphinobenzyl)-N-phenylamine (PNP) (1), bis(2-diphenylphosphinobenzyl) ether (POP) (2) and their coordination chemistry with copper(I) halides.

    4. Magnesium Phosphors

      Tunable Blue–Red Emission and Energy-Transfer Properties of Mg3(PO4)2:­Eu2+,­Mn2+ Phosphors

      Zheng Zhang and Wanjun Tang

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500236

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      Mg3(PO4)2:Eu2+,Mn2+ phosphors with blue and red emission bands are synthesized. Mg3(PO4)2 has two Mg2+ sites for the Eu2+ ions to occupy; therefore, they form two emission centers. Energy transfer from Eu2+ to Mn2+ ions occurs, and the transfer mechanism is determined. The Mn2+ 4T1[RIGHTWARDS ARROW]6A1 emission band of Mg3(PO4)2:Eu2+,Mn2+ shows a redshift owing to exchange interactions between the Mn2+ ions.

    5. Redox Mediators in DSSCs

      Dye-Sensitized Solar-Cell Performance of a Cobalt(III/II) Redox Mediator with the 2,6-Bis(8-quinolinyl)pyridine Ligand

      Nicholas A. Lee, Blaise A. Frenzel, Jonathan Rochford and Sean E. Hightower

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500461

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      Electrochemical properties of the [Co(bqp)2]3+/2+ redox mediator is evaluated in a dye-sensitized solar-cell (DSSC) device with the MK-2 dye photosensitizer. A comparable photovoltaic efficiency is observed for [Co(bqp)2]3+/2+ (η = 3.73 %) vs. the established [Co(tpy)2]3+/2+ mediator (η = 4.47 %).

    6. Photosensitizers

      Ruthenium Imidazophenanthrolinium Complexes with Prolonged Excited-State Lifetimes

      Robert Staehle, Christian Reichardt, Jürgen Popp, Dieter Sorsche, Lydia Petermann, Katharina Kastner, Carsten Streb, Benjamin Dietzek and Sven Rau

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500021

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      A series of ruthenium polypyridyl complexes containing an imidazolium-functionalized phenanthroline ligand are presented. The complexes are fully characterized, and their solid-state structures are determined. The influence of the new ligand is investigated through absorption and emission spectroscopy, cyclic voltammetry, and resonance Raman spectroscopy investigations.

  6. Short Communications

    1. Terminal Phosphinidenes

      The Reaction of Terminal Phosphinidene Complexes [RP–W(CO)5] with Vinylbor­onic Acids: Cycloaddition vs. P–C Bond Formation

      Yong Xiang Ng and François Mathey

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500594

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      Terminal phosphinidene complexes react with vinylboronic acid to give the expected phosphirane complexes, but the addition of K3PO4 changes the course of the reaction, and secondary vinylphosphine complexes are obtained instead.

  7. Full Papers

    1. Twin Polymerization

      Si(OCH2Fc)4: Synthesis, Electrochemical Behavior, and Twin Polymerization

      Christian Schliebe, Ulrike Pfaff, Thomas Gemming, Charles Lochenie, Birgit Weber and Heinrich Lang

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500464

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      The straightforward preparation of iron-rich porous carbon and silica materials by twin polymerization of Si(OCH2Fc)4 [Fc = Fe(η5-C5H4)(η5-C5H5)] and 2,2′-spirobi[4H-1,3,2-benzodioxasiline] is reported; the electrochemical properties of Si(OCH2Fc)4 are discussed.

    2. Phosphacyclobutadiene Complexes

      Cobalt(I) and Nickel(II) Complexes of Bis(1,3-diphosphacyclobutadiene) Sandwich Anions

      Christian Rödl and Robert Wolf

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500583

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      Dinuclear diphosphacyclobutadiene complexes have been synthesized by transmetalating the thallium(I) salt [Tl(thf)2{Co(P2C2tBu2)2}] with organometallic cobalt(I) and nickel(II) halides. The structural, spectroscopic, and redox properties of two new bimetallic complexes are presented, and their electronic structures are analyzed by DFT calculations.

    3. Silsesquioxane

      An Efficient Approach to Octabromophenylethyl-Functionalized Cage Silsesquioxane and Its Use in Constructing Hybrid Porous Materials

      Chundong Jiang, Wenyan Yang, Liguo Li, Yuqi Hou, Xiaoling Zhao and Hongzhi Liu

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500462

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      Octabromophenylethyl-functionalized cage silsesquioxane (BrPh-SQ) is successfully prepared through a green and efficient approach involving the Friedel–Crafts alkylation of octavinylsilsesquioxane (OVS) with bromobenzene. BrPh-SQ can be utilized as a building block to construct a hybrid porous material with OVS by the Heck reaction.

  8. Microreviews

    1. Bioinorganic Interfaces

      Understanding and Tuning Bioinorganic Interfaces for the Design of Bionanocomposites

      Hugo Voisin, Carole Aimé and Thibaud Coradin

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500403

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      Understanding and controlling interfacial interactions between biological molecules – from lipids to proteins – and inorganic nano-objects, polyoxometallates and colloids allows the synthesis of bionanocomposites with applications in biotechnology and biomedicine.

  9. Full Papers

    1. Carbonyl Clusters

      Synthesis and Reactivity of Ruthenium–Antimony Carbonyl Clusters

      Ying-Zhou Li, Rakesh Ganguly, Weng Kee Leong and Yang Liu

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500522

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      A series of ruthenium–antimony carbonyl clusters are prepared by the oxidative addition of Sb–Cl or Sb–Sb bonds to lightly stabilized ruthenium carbonyl clusters. Their solid- and solution-state structures are studied in detail by X-ray crystallography and variable-temperature multinuclear NMR experiments, respectively.

    2. Antitumor Complexes

      Heterodi- (Fe, Pd/Pt) and Heterotrimetallic (Fe2, Pd) Complexes Derived from 4-(Ferrocenylmethyl)-N-(2-methoxyethyl)-3,5-­diphenylpyrazole as Potential Antitumoral Agents

      Eva Guillén, Asensio González, Concepción López, Pradipta K. Basu, Amrita Ghosh, Mercè Font-Bardía, Carme Calvis and Ramón Messeguer

      Article first published online: 8 JUL 2015 | DOI: 10.1002/ejic.201500520

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      The bifunctional role of new ferrocene–pyrazole compound as a ligand for PdII or PtII complexes and as a potent antitumor agent is investigated.

  10. Microreviews

    1. Silylated Ylenes

      Silylated Group 14 Ylenes: An Emerging Class of Reactive Compounds

      Christoph Marschner

      Article first published online: 8 JUL 2015 | DOI: 10.1002/ejic.201500495

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      Silyl-substituted heavy-element tetrylenes are reactive species that either dimerize or undergo rearrangement of some kind. Trapping them as phosphine adducts prevents dimerization and allows study of the reactivity of the free tetrylenes and their introduction as ligands into transition-metal complexes.

  11. Full Papers

    1. Molybdenum Oxide Thin Films

      A Hierarchical MoO2/Au/MnO2 Hetero­structure with Enhanced Electrochemical Performance for Application as Supercapacitor

      Xia Zhang, Yuandong Xu, Ying Ma, Min Yang and Yanxing Qi

      Article first published online: 8 JUL 2015 | DOI: 10.1002/ejic.201500501

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      A hierarchical MoO2/Au/MnO2 heterostructure was fabricated by a two-step electrodeposition method. It displayed excellent long-term cycling stability and high rate capability for application as supercapacitor.

    2. Epoxidation

      Silver-Based 4A Zeolite Composite Catalyst for Styrene Epoxidation by One-Pot Hydrothermal Synthesis

      Xiaosong Hu, Jie Bai, Chunping Li, Haiou Liang and Weiyan Sun

      Article first published online: 8 JUL 2015 | DOI: 10.1002/ejic.201500443

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      A one-pot hydrothermal method is used to synthesize a silver-based 4A zeolite composite catalyst for styrene epoxidation. A silver/ammonia solution is mixed with poly(ethylene glycol). Then, the mixture is added to the aging system, which contains the crystal nucleus of 4A zeolite, and absolute ethyl alcohol is added to the system. Finally, the composite catalyst is obtained by crystallization.

    3. Electrode Materials

      Synthesis and Characterization of α-­NiMoO4 Nanorods for Supercapacitor ­Application

      Palani Raja Jothi, Kannan Shanthi, Rahul R. Salunkhe, Malay Pramanik, Victor Malgras, Saad M. Alshehri and Yusuke Yamauchi

      Article first published online: 8 JUL 2015 | DOI: 10.1002/ejic.201500410

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      We report the synthesis of electrode materials based on 1D α-NiMoO4 nanorods for application as a supercapacitor. The nanorod morphology can be easily controlled by optimizing the initial reaction conditions. Thus, this simple chemical approach to the synthesis of binary metal oxides could be extended to other metal oxides and lead to promising performances in energy storage applications.

    4. Polyoxometalates

      Electro-Assisted Reduction of CO2 to CO and Formaldehyde by (TOA)6[α-SiW11O39Co(_)] Polyoxometalate

      Marcelo Girardi, Sébastien Blanchard, Sophie Griveau, Philippe Simon, Marc Fontecave, Fethi Bedioui and Anna Proust

      Article first published online: 8 JUL 2015 | DOI: 10.1002/ejic.201500389

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      The cobalt derivative of the silico-undecatungstate [α-SiW11O39Co(_)]6– is a catalyst for the multiproton-multielectron electrochemical reduction of CO2, with unique selectivity. Analysis of electrolysis products in the gas and liquid phases shows the formation of CO and HCHO without detection of H2.

    5. Dinuclear Nitrato Complexes

      Dinuclear Nitrato Coordination Compounds with Bis(3,5-tert-butylpyrazol-1-yl)­acetate

      Bojan Kozlevčar, Klemen Jakomin, Marta Počkaj, Zvonko Jagličić, Andreas Beyer, Nicolai Burzlaff and Nives Kitanovski

      Article first published online: 8 JUL 2015 | DOI: 10.1002/ejic.201500368

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      Two dinuclear compounds with the bis(3,5-tert-butylpyrazol-1-yl)acetic acid anion (bdtbpza), [Co(NO3)(bdtbpza)]2 (1) and [Cu(NO3)(bdtbpza)]2 (2), are reported. Nitrato coligands are present instead of the commonly observed chlorido anions in dinuclear species with MO2N2O chromophores; 1 is distorted trigonal bipyramidal, and 2 is square pyramidal. Antiferromagnetic coupling is seen only in 1.

    6. Telluroether Complexes

      Pt, Pd and Hg Complexes with Potentially Tridentate Telluroether Ligands

      Lars Kirsten, Vania D. Schwade, Lars Selter, Adelheid Hagenbach, Paulo C. Piquini, Ernesto Schulz Lang and Ulrich Abram

      Article first published online: 8 JUL 2015 | DOI: 10.1002/ejic.201500365

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      Reactions between MCl2 (M = Pt, Pd, Hg) and potentially tridentate telluroether ligands with additional picolinamido or thiocarbamoylbenzamidinato units give neutral chelates. Long-range Te···M, Te···halide, or Te···S interactions assemble the obtained molecules to dimeric and/or polymeric arrangements in the solid state.

    7. Upconversion Nanomaterials

      The Effects of Morphology and Linker Length on the Properties of Peptide–Lanthanide Upconversion Nanomaterials as G2 Phase Cell Cycle Inhibitors

      Chi-Fai Chan, Chen Xie, Ming-Kiu Tsang, Sam Lear, Lixiong Dai, Yan Zhou, Jakub Cicho, Miroslaw Karbowiak, Dariusz Hreniak, Rongfeng Lan, Steve L. Cobb, Michael Hon-Wah Lam, Jianhua Hao and Ka-Leung Wong

      Article first published online: 8 JUL 2015 | DOI: 10.1002/ejic.201500321

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      Plk1-specific peptides are bioconjugated onto spherical and cubic NaGdF4@SiO2 nanoparticles, and the inhibitory effects of the hybrid materials towards normal cells and cancer cells are investigated.

    8. ZnO Nanocrystals

      Production and Photoelectric Activity of P and Al Co-Doped ZnO Nanomaterials

      Ya-Juan Deng, Yi Lu, Jin-Ku Liu and Xiao-Hong Yang

      Article first published online: 8 JUL 2015 | DOI: 10.1002/ejic.201500246

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      Phosphorus and aluminium co-doped conductive zinc oxide nanocrystals (PAZO NCs) with novel visible-light catalytic activities have been mass produced by the combustion method. The size of PAZO NCs decreased with increasing doping of phosphorus and aluminium. The 3PAZO (molar ratio of Zn to P atoms is 100:3) NCs showed the best visible-light catalytic efficiency of the PAZO NCs.

    9. Luminescent Ir(III) Chromophores

      Protonation-Dependent Luminescence of an Iridium(III) Bibenzimidazole Chromophore

      Sebastian A. Rommel, Dieter Sorsche, Nils Rockstroh, Frank W. Heinemann, Joachim Kübel, Maria Wächtler, Benjamin Dietzek and Sven Rau

      Article first published online: 8 JUL 2015 | DOI: 10.1002/ejic.201500234

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      The syntheses of the bis(phenylpyridine)iridium(III) complex of 4,4′,5,5′-tetraethyl-2,2′-bibenzimidazole [Ir(tmBBI)-Hx] and the homodinuclear complex [Ir(tmBBI)Ir] are described. The structures are determined by single-crystal X-ray diffraction analysis and NMR spectroscopy, and detailed UV/Vis and emission spectroscopy studies are performed.

    10. Solid-State Transformations

      Probing Solid-State Breathing and Structural Transformations in a Series of Silver(I) Porous Coordination Polymers

      Witold M. Bloch and Christopher J. Sumby

      Article first published online: 2 JUL 2015 | DOI: 10.1002/ejic.201500647

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      Herein two new examples of an AgI porous coordination polymer that display solid-state breathing are reported. Additional transformations of these materials to non-porous 2D and 3D structures are investigated.

    11. Luminescent Silicate Nanoparticles

      Insight into CaMgSi2O6:Eu2+,Mn2+,Dy3+ Nanoprobes: Influence of Chemical Composition and Crystallinity on Persistent Red Luminescence

      Céline Rosticher, Bruno Viana, Guillaume Laurent, Patrick Le Griel and Corinne Chanéac

      Article first published online: 2 JUL 2015 | DOI: 10.1002/ejic.201500257

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      Nanoparticles of CaxMgySi2O6 doped with Eu2+, Mn2+, and Dy3+ have been prepared with a high production yield by a sol–gel method inspired by the Stöber process with the aim of improving the luminescent properties and decreasing the size of silicate-based nanoprobes. Such a study is essential to promote the emergence of these nanoprobes in the field of optical imaging.

    12. Magnetic Nanohybrids

      Synthesis of Stable Magnetic Polyaniline Nanohybrids with Pyrene as a Cross-Linker for Simultaneous Diagnosis by Magnetic Resonance Imaging and Photothermal Therapy

      Taeksu Lee, Doyeon Bang, Yeonji Park, Young Wook Chang, Byunghoon Kang, Jinyoung Kim, Jin-Suck Suh, Yong-Min Huh and Seungjoo Haam

      Article first published online: 2 JUL 2015 | DOI: 10.1002/ejic.201500283

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      Magnetic polyaniline nanoparticles (MPANs) are synthesized and show evenly mixed magnetic nanoparticles (MNPs) and polyaniline (PANI) with increased colloidal stability owing to the hydrophobic and π–π interactions between the PANI and pyrene molecules.

    13. Metal Chelating Agents

      Mercury Complexes with Tripodal Pseudopeptides Derived from D-Penicillamine Favour a HgS3 Coordination

      Anne-Solène Jullien, Christelle Gateau, Colette Lebrun and Pascale Delangle

      Article first published online: 1 JUL 2015 | DOI: 10.1002/ejic.201500421

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      Tripodal pseudopeptides anchored on a nitrilotriacetic chemical scaffold and extended with three D-penicillamine units stabilize the unusual HgS3 coordination over a large pH range in a hindered coordination environment.

    14. Sensors

      Off–On, Ratiometric, and On–Off Fluorescence Responses of Thioether-Linked Bisquinolines toward Hg2+ and Fe3+ Ions

      Yuji Mikata, Kaori Nakanishi, Fumie Nakagaki, Asako Kizu and Hideo Konno

      Article first published online: 1 JUL 2015 | DOI: 10.1002/ejic.201500220

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      The selectivity of fluorescent bisquinoline derivatives with thioether linkers for Hg2+ ions is improved by 8-quinolylmethyl tethering and increasing the number of sulfur atoms through the extension of the linker.

    15. Ti and V Coordination Chemistry

      Synthesis and Characterisation of Various Diester and Triester Adducts of TiCl4

      Ben J. Blackburn, Jared H. Crane, Caroline E. Knapp, Peter Marchand, David Pugh, Ivan P. Parkin and Claire J. Carmalt

      Article first published online: 30 JUN 2015 | DOI: 10.1002/ejic.201500471

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      The synthesis of novel titanium complexes with triesters and diesters was achieved using Schlenk techniques for the purpose of ellucidating the previously unknown mechanisms at play during the industrially used Chloride Process.

    16. ZnO Thin Films

      Aerosol-Assisted Chemical-Vapour Deposition of Zinc Oxide from Single-Source β-Iminoesterate Precursors

      Joe A. Manzi, Caroline E. Knapp, Ivan P. Parkin and Claire J. Carmalt

      Article first published online: 30 JUN 2015 | DOI: 10.1002/ejic.201500416

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      The synthesis, isolation and characterisation of zinc β-iminoesterate precursors of the type [Zn(CH3C(NR)CHC(O)OCH2CH3)] are described, as well as their use for the first time in the aerosol-assisted chemical-vapour deposition (AACVD) of ZnO thin films at 450 °C. Results show that changing the R group on the N moiety of the precursors has a significant effect on carbon contamination in the films.

    17. Thermoelectric Nitride Materials

      Origin of Projected Excellent Thermoelectric Transport Properties in d0-Electron AMN2 (A = Sr or Ba; M = Ti, Zr, Hf) Layered Complex Metal Nitrides

      Isao Ohkubo and Takao Mori

      Article first published online: 30 JUN 2015 | DOI: 10.1002/ejic.201500350

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      d0-Electron layered complex metal nitrides (AMN2) are expected to exhibit excellent thermoelectric properties that arise from their electronic structures and small effective masses.

  12. Microreviews

    1. Phosphovanadomolybdates

      Mo-V-Phosphoric Heteropoly Acids and Their Salts: Aqueous Solution Preparation – Challenges and Perspectives

      Victor F. Odyakov, Elena G. Zhizhina, Yulia A. Rodikova and Leonid L. Gogin

      Article first published online: 29 JUN 2015 | DOI: 10.1002/ejic.201500359

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      Preliminary V2O5 activation by addition of hydrogen peroxide H2O2 allows one to obtain vanadium-containing heteropoly acid (HPA) solutions directly from V2O5, MoO3, and H3PO4 without extraneous components. Such a synthetic pathway, named a peroxide route, offers a promising ecological method for preparing valuable Mo-V-P HPAs in short reaction times on a large scale.

  13. Full Papers

    1. Dye-Sensitized Solar Cells

      Dye-Sensitized Solar Cells with Biferrocenyl Antennae Having Quinoxaline Spacers

      Ratna Chauhan, Mohammad Shahid, Manoj Trivedi, Dinesh P. Amalnerkar and Abhinav Kumar

      Article first published online: 29 JUN 2015 | DOI: 10.1002/ejic.201500488

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      Four biferrocenyl quinoxaline derivatives are synthesized and their light-harvesting properties are explored. Dyes having Cl, NO2, and COOH substituents on the spacers show the best photovoltaic performance, and this may be attributed to their ability to accept high loadings of the dye on the TiO2 surface and the long lifetime of electrons in the TiO2 conduction band.

    2. Near-Infrared Dyes

      Azadipyrromethene-Based Near-Infrared Dyes: Effect of Thienylethynyl Substitution at the Distal and Proximal Phenyl Groups

      Cassie M. Daddario, Qi Han, Matthias Zeller and Geneviève Sauvé

      Article first published online: 25 JUN 2015 | DOI: 10.1002/ejic.201500348

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      Azadipyrromethene ligands substituted with thienylethynyl substituents at the distal or proximal phenyl groups were synthesized and coordinated with BF2+ and ZnII. Thienylethynyl substitutions redshift the absorption spectra of the dyes, with a larger shift for proximal substitution. Substitutions also stabilize the anions, and the placement of the thienylethynyl groups do not affect the reduction potentials.

  14. Short Communications

    1. Glycerodendrimers

      Platinum Nanoparticles Stabilized by Glycerodendrimers: Synthesis and Application to the Hydrogenation of α,β-Unsaturated Ketones under Mild Conditions

      Bérengère Menot, Lionel Salmon and Sandrine Bouquillon

      Article first published online: 24 JUN 2015 | DOI: 10.1002/ejic.201500530

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      Pt nanoparticles are stabilized by glycerodendrimers (GD) and used (and recycled) for the reduction of α,β-unsaturated ketones to saturated ketones at room temperature in water under H2 (101.3 kPa).

  15. Full Papers

    1. Bimodal MRI Agents

      Magnetofluorescent Nanoaggregates Incorporating Terbium(III) Complexes as Potential Bimodal Agents for Magnetic Resonance and Optical Imaging

      Michael Harris, Sophie Carron, Luce Vander Elst, Sophie Laurent and Tatjana N. Parac-Vogt

      Article first published online: 23 JUN 2015 | DOI: 10.1002/ejic.201500310

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      Magnetofluorescent nanoaggregates incorporating amphiphilic terbium(III) complexes are created and their potential as bimodal agents for magnetic resonance and optical imaging are examined.

    2. Nanophosphors

      Uniform Poly(acrylic acid)-Functionalized Lanthanide-Doped LaVO4 Nanophosphors with High Colloidal Stability and Biocompatibility

      Nuria O. Nuñez, Paola Zambrano, Jorge García-Sevillano, Eugenio Cantelar, Sara Rivera-Fernández, Jesús M. de la Fuente and Manuel Ocaña

      Article first published online: 22 JUN 2015 | DOI: 10.1002/ejic.201500265

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      Uniform lanthanide-doped LaVO4 nanospheres functionalized with poly(acrylic acid) are synthesized with a controllable size by a one-pot procedure. As these nanoparticles present strong red (Eu) or near-infrared (Nd) luminescence, are nontoxic for cells, and show high colloidal stability in physiological buffer, they are good candidates as optical biomarkers for in vitro applications.

  16. Short Communications

    1. Bridging Thiadiazole Ligands

      A Family of Dinuclear Iron(II) SCO Compounds Based on a 1,3,4-Thiadiazole Bridging Ligand

      Christian F. Herold, Luca M. Carrella and Eva Rentschler

      Article first published online: 12 JUN 2015 | DOI: 10.1002/ejic.201500483

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      Herein we present a new 1,3,4-thiadiazole bridging ligand and three spin-crossover active dinuclear iron(II) compounds. The complexes show promising magnetic properties with a diamagnetic [LS–LS] ground state at low temperatures and represent a great starting point to explore this new family of dinuclear SCO compounds.

  17. Full Papers

    1. Reactivity of Red Phosphorus

      Unexpected Reactivity of Red Phosphorus in Ionic Liquids

      Matthias F. Groh, Silvia Paasch, Alexander Weiz, Michael Ruck and Eike Brunner

      Article first published online: 3 JUN 2015 | DOI: 10.1002/ejic.201500502

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      Red phosphorus readily reacts with iodine in a Lewis-acidic ionic liquid at moderate temperature. Besides iodides, phosphorus nanoparticles are formed. The latter are also obtained in a bottom-up process starting from P2I4. In situ liquid- and solid-state NMR spectroscopy reveals details of the reactions.

    2. Multimodal Imaging

      Patent Blue Derivatized Dendronized Iron Oxide Nanoparticles for Multimodal Imaging

      Lai Truong-Phuoc, Marie Kueny-Stotz, Julien Jouhannaud, Antonio Garofalo, François-Xavier Blé, Hervé Simon, Franklin Tellier, Patrick Poulet, Piero Chirco, Sylvie Begin-Colin, Geneviève Pourroy and Delphine Felder-Flesch

      Article first published online: 2 JUN 2015 | DOI: 10.1002/ejic.201500289

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      Iron oxide particles of 10 and 20 nm diameter, dendronized and derivatized with Patent Blue VF dye, survived subcutaneous injection for bimodal lymph node detection with a hand-held probe during surgery.

    3. Magnetic Colloids

      Long-Term Stability and Reproducibility of Magnetic Colloids are Key Issues for Steady Values of Specific Power Absorption Over Time

      Beatriz Sanz, M. Pilar Calatayud, Nicolás Cassinelli, M. Ricardo Ibarra and Gerardo F. Goya

      Article first published online: 2 JUN 2015 | DOI: 10.1002/ejic.201500303

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      The poly(ethyleneimine)-coated magnetic nanoparticles (PEI-MNPs) prepared in this work by oxidative hydrolysis show good reproducibility of size and size distribution. In addition, these PEI-MNPs show only a moderate decrease in the specific power absorption when they aggregate over time. These results render these particles suitable for applications in magnetic hyperthermia.

    4. Silanechalcogenones

      Acyclic Amido-Containing Silanechalcogenones

      Yuk-Chi Chan, Yongxin Li, Rakesh Ganguly and Cheuk-Wai So

      Article first published online: 27 MAY 2015 | DOI: 10.1002/ejic.201500108

      Thumbnail image of graphical abstract

      Reactions of the amidinate-stabilized silicon(II) bis(trimethylsilyl)amide [LSiN(SiMe3)2], {L = PhC(NtBu)2, 1} with a stiochiometric amount of elemental sulfur, selenium and tellurium afforded the first stable silanechalcogenones comprising an acyclic amido substituent, [L{N(SiMe3)2}Si=E] {E = S (2), Se (3) or Te (4)}.

  18. Microreviews

    1. Bio-Inspired Si Coatings

      Bio-Inspired Formation of Silica Thin Films: From Solid Substrates to Cellular Interfaces

      Woo Kyung Cho and Sung Ho Yang

      Article first published online: 19 MAY 2015 | DOI: 10.1002/ejic.201500308

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      The bio-inspired formation of silica thin films on the surfaces of flat solids, microparticles, nanoparticles, and living cells is reviewed.

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