European Journal of Inorganic Chemistry

Cover image for Vol. 2014 Issue 36

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

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.965

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

Online ISSN: 1099-0682

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

VIEW

  1. 1 - 71
  1. Full Papers

    1. Low-Coordinate Carbene Complexes

      1,8-Disubstituted Xanthylidene-Based Remote Carbenes: Photolytic Generation and Isolation of Low-Coordinate Palladium(II) Complex

      Shun Sugawara, Manabu Abe, Yoshihisa Fujiwara, Masayuki Wakioka, Fumiyuki Ozawa and Yohsuke Yamamoto

      Article first published online: 18 DEC 2014 | DOI: 10.1002/ejic.201403017

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      The photolysis-induced formation of 1,8-disubstituted xanthylidene-based remote carbenes from tosylhydrazone lithium salts has been investigated. The 1,8-unsubstituted carbene was found to be kinetically more reactive than the parent xanthylidene. Oxidative addition of palladium(0) to the chloride precursor facilitated the isolation of a low-coordinate 14-electron palladium(II)–carbene complex.

    2. Pd-Catalyzed C–C Coupling Reactions

      Catalytic Synthesis of Bi- and Teraryls in Aqueous Medium with Palladium(II) Complexes of 2-(Pyridine-2-ylmethylsulfanyl)benzoic Acid

      Om Prakash, Hemant Joshi, Kamal Nayan Sharma, Alpesh Kumar Sharma and Ajai K. Singh

      Article first published online: 18 DEC 2014 | DOI: 10.1002/ejic.201403003

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      Complexes [PdCl2L1] [1, L1 = 2-(pyridine-2-ylmethyl)sulfanylbenzoic acid] and [Pd(L2-H)2] (2, L2-H = 2-pyridin-2-yl-benzo[b]thiophen-3-ol) catalyze Suzuki coupling (1 in water) reactions to form bi- and teraryls. L2 forms by an unprecedented cyclization of L1. Pd nanoparticles (NPs) generated in situ play a role in the catalysis, which is a combination of homogeneous and heterogeneous processes.

    3. Ternary Semiconductor Precursors

      1,2-Dithiooxalato-Bridged Heterobimetallic Complexes as Single-Source Precursors for Ternary Metal Sulfide Semiconductors

      Mathias Nowotny, Sabine Foro, Silvio Heinschke, Rudolf C. Hoffmann and Jörg J. Schneider

      Article first published online: 18 DEC 2014 | DOI: 10.1002/ejic.201402990

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      Bimetallic single-source precursor complexes for ternary metal sulfide semiconductors are presented. The 1,2-dithiooxalato ligand serves as a linker, complexation site, and molcular source of sulfur in the formation of CuInS2 nanoparticles.

    4. Seleno- and Telluroether as Ligands

      Structural Variation in [PdX2{RE(CH2)nNMe2}] (E = Se, Te; X = Cl, OAc) Complexes: Experimental Results, Computational Analysis, and Catalytic Activity in Suzuki Coupling Reactions

      Dilip K. Paluru, Sandip Dey, Amey Wadawale, Dilip K. Maity, Nattamai Bhuvanesh and Vimal K. Jain

      Article first published online: 18 DEC 2014 | DOI: 10.1002/ejic.201402943

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      Complexes [PdX2{RE(CH2)nNMe2}]m (X = Cl, OAc) exist in one monomeric and two dimeric forms in solution depending on E and n. Molecular structures were established by X-ray structural analyses and supported by DFT calculations. These complexes act as catalyst in Suzuki coupling reactions.

    5. Lanthanide Luminescence

      Synthesis, Stability and Sensitised Lanthanide Luminescence of Heterobimetallic d/f Terpyridine Complexes

      Evan G. Moore, Massimo Benaglia, Giacomo Bergamini and Paola Ceroni

      Article first published online: 16 DEC 2014 | DOI: 10.1002/ejic.201403100

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      The synthesis and solution properties for a series of heterobimetallic RuII–LnIII complexes are reported. These compounds demonstrate the use of a RuII bis-terpyridine unit as the sensitiser for LnIII-based near-infrared emission for the first time. Energy transfer is shown to operate through both the triplet ligand-centred and triplet metal-to-ligand charge-transfer pathways.

    6. Luminescent Ionic Liquids

      Structures and Properties of Luminescent Pentanitratoeuropate(III) Ionic Liquids

      Ying Zhao, Ling He, Ning Tang, Song Qin, Guo-Hong Tao and Fu-Xin Liang

      Article first published online: 16 DEC 2014 | DOI: 10.1002/ejic.201403018

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      A series of luminescent ionic liquids based on pentanitratoeuropate (III) anions are synthesized and characterized. These complexes exhibit high thermostability and a wide liquidus range. The 10-coordinate [Eu(NO3)5]2– anion has a highly symmetric trigonal-bipyramidal structure. Complexes 16 exhibit bright red luminescence with narrow-band and intense emission of high colorimetric purity.

    7. Spin-Crossover Complexes

      Iron(II) Spin-Crossover Complexes with Schiff Base Like Ligands and N-Alkylimidazoles

      Stephan Schlamp, Charles Lochenie, Tobias Bauer, Rhett Kempe and Birgit Weber

      Article first published online: 16 DEC 2014 | DOI: 10.1002/ejic.201403021

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      Iron(II) spin-crossover complexes with Schiff base like equatorial ligands and alkylimidazole axial ligands are synthesised. The alkyl chain length is varied from 5 to 7 and 10 carbon atoms. The crystal structures of the C7 and C10 compounds are described. There is an increased cooperativity in spin-crossover behaviour for the compound with the longer C10 alkyl chain than for the C5 compound.

    8. Polyoxometalates

      Three Polyoxometalate-Based Coordination Polymers Constructed from the Same Dimetallic Cyclic Building Block

      Min Gu, Yuanhang Ren, Yichen Hu, Min Tang, Zuping Kong, Bin Yue and Heyong He

      Article first published online: 15 DEC 2014 | DOI: 10.1002/ejic.201402938

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      Three polyoxometalate-based (POM-based) coordination polymers containing a similar type of building block, [M2(3-bpo)2(C5H4NCOOH)2]4+ [M = Cu, Co, Ni; 3-bpo = 2,5-bis(3-pyridyl)-1,3,4-oxadiazole], are hydrothermally synthesized. These polymers are characterized, and their electrochemical behaviors are studied by cyclic voltammetry.

    9. Coupling Reactions

      Synthesis and Reactions of PdII Complexes with Aryl, Aroyl, and Iminoaroyl Ligands – Insertion of CO and RNC into the Pd–Ar Bond and Intermolecular Coupling of the Ligands

      Yuji Suzaki, Masanori Shirokawa, Takeyoshi Yagyu and Kohtaro Osakada

      Article first published online: 15 DEC 2014 | DOI: 10.1002/ejic.201402720

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      Aryl-, aroyl-, and iminoaroyl iodidopalladium(II) complexes with a 2,2′-bipyridine ligand react with AgBF4 and H2O to afford biaryls, diarylketones, and arylamides by labilization of the iodido ligand.

    10. Perovskite Nanoparticles

      Synthesis of Monodisperse SrTi1–xZrxO3 Nanocubes in Oleate by a Two-Phase Solvothermal Method

      Christian Friderichs, Nikolay Zotov and Werner Mader

      Article first published online: 12 DEC 2014 | DOI: 10.1002/ejic.201402724

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      Alkali metal oleate formed in situ in an oil/water solvothermal process is a suitable reaction medium for the synthesis of monodisperse SrTi1–xZrxO3 perovskite nanoparticles, which are characterized in detail by TEM methods as well as XRD and Raman spectroscopy to provide information on their crystal structure and surface termination.

    11. Palladium Recovery

      Hexagonal-Prism-Shaped Optical Sensor/Captor for the Optical Recognition and Sequestration of PdII Ions from Urban Mines

      Mohamed A. Shenashen, Sherif A. El-Safty, Emad A. Elshehy and Mohamed Khairy

      Article first published online: 12 DEC 2014 | DOI: 10.1002/ejic.201402756

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      We report the pressure-assisted fabrication of a hexagonal-prism-shaped optical sensor/captor (OSC) based on monolithic aluminosilica scaffolds. The H-aggregates of the probe might lead to the formation of 1D molecular probe assemblies parallel to the interior pore walls. This OSC is a promising technology for the efficient recognition, removal, and recovery of PdII ions from urban mines.

    12. Carbon Dioxide Reduction

      Photo- and Electrocatalytic Reduction of CO2 by [Re(CO)3{α,α′-Diimine-(4-piperidinyl-1,8-naphthalimide)}Cl] Complexes

      Federico Franco, Claudio Cometto, Claudio Garino, Claudio Minero, Fabrizio Sordello, Carlo Nervi and Roberto Gobetto

      Article first published online: 12 DEC 2014 | DOI: 10.1002/ejic.201402912

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      The efficiency and stability of a series of [Re(α,α′-diimine)(CO)3Cl] complexes suitable for catalytic photo- and electrochemical selective reduction of CO2 to CO has been investigated. The introduction in the diimine part of the fluorescent moiety 4-piperidinyl-1,8-naphthalimide provides new insights into designing catalysts with improved performance.

  2. Short Communications

    1. The Pentafluorosulfanyl Substituent

      Pentafluorosulfanyltrimethylsilane: A Nonexistent Molecule?

      Abhik Ghosh and Jeanet Conradie

      Article first published online: 11 DEC 2014 | DOI: 10.1002/ejic.201402928

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      According to DFT calculations, reagents such as Me3SiSF5, LiSF5 and CuSF5 are all thermodynamically and kinetically unstable. Attempts to synthesize them are therefore doomed to failure.

  3. Microreviews

    1. Methylalumoxane

      Methylalumoxane – History, Production, Properties, and Applications

      Harmen S. Zijlstra and Sjoerd Harder

      Article first published online: 11 DEC 2014 | DOI: 10.1002/ejic.201402978

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      This is a comprehensive overview on methylalumoxane (MAO). After presenting its historical discovery and development, the review focuses on the synthesis and large-scale production of MAO, its structural characterization, properties, and different roles in the activation of olefin polymerization catalysts. Potential modifications, immobilization on surfaces, and other applications are also mentioned.

  4. Full Papers

    1. Phosphorus Heterocycles

      Reactivity of Aromatic Phosphorus Heterocycles – Differences Between Nonfunctionalized and Pyridyl-Substituted 2,4,6-Triarylphosphinines

      Gregor Pfeifer, Philippe Ribagnac, Xavier-Frédéric Le Goff, Jelena Wiecko, Nicolas Mézailles and Christian Müller

      Article first published online: 11 DEC 2014 | DOI: 10.1002/ejic.201403048

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      Substantial differences in reactivity towards methanol have been observed for 2,4,6-triarylphosphinine derivatives. The outcomes of the transformations strongly depend on the presence of additional donor functionalities within the phosphorus heterocycle as well as the nature of the solvent and the reaction temperature. DFT calculations were performed to rationalize the observed reaction pathways.

    2. Alkali Metal Complexes

      Structural Diversity in Sterically Demanding Diiminophosphinato Alkali Metal Complexes

      Andrew L. Hawley and Andreas Stasch

      Article first published online: 11 DEC 2014 | DOI: 10.1002/ejic.201402924

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      We report on the synthesis of a new aminoiminophosphorane and a range of homoleptic alkali metal complexes of sterically demanding diiminophosphinate ligands, plus a series of related THF-solvated alkali metal complexes that show a rich structural diversity between them and underpin the flexible coordination properties of that ligand class.

    3. Influence of Ligand Substitution Pattern on Structure in Cobalt(II) Complexes of Bulky N,N′-Diarylformamidinate N-Oxides

      Mihaela Cibian, Sophie Langis-Barsetti, Fernanda Gomes De Mendonça, Sammy Touaibia, Sofia Derossi, Denis Spasyuk and Garry S. Hanan

      Article first published online: 10 DEC 2014 | DOI: 10.1002/ejic.201402895

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      Cobalt(II) bis(chelates) of bulky N,N′-diarylformamidinate N-oxide ligands show isomerization from square-planar low-spin (in the solid state) to tetrahedral high-spin (in solutions of noncoordinating solvents).

    4. Rare Earth Cyanurates

      Synthesis, Structure, and Luminescence of Rare Earth Cyanurates

      Markus Kalmutzki, Markus Ströbele, David Enseling, Thomas Jüstel and H.-Jürgen Meyer

      Article first published online: 10 DEC 2014 | DOI: 10.1002/ejic.201402697

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      Rare earth metal cyanurates were prepared by solid-state metathesis reactions and characterized as ARE2Cl(O3C3N3)2 (A = K, Rb, Cs and RE = La, Ce, Pr). Photoluminescence properties of Eu3+ and Tb3+ doped RbRE2Cl(O3C3N3)2 samples were studied by means of luminescence and reflection spectroscopy.

    5. Slow Magnetic Relaxation

      Slow Magnetic Relaxation in Mononuclear Octahedral Manganese(III) Complexes with Dibenzoylmethanide Ligands

      Lei Chen, Jing Wang, Yuan-Zhong Liu, You Song, Xue-Tai Chen, Yi-Quan Zhang and Zi-Ling Xue

      Article first published online: 9 DEC 2014 | DOI: 10.1002/ejic.201402964

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      Three mononuclear MnIII complexes based on the dibenzoylmethanido ligand and having negative zero-field-splitting parameters D exhibit field-induced slow relaxation behavior.

    6. Uranyl–Organic Hybrids

      Uranyl–Organic Hybrids Designed from Hydroxyphosphonate

      Pius O. Adelani, Nicholas A. Martinez, Nathaniel D. Cook and Peter C. Burns

      Article first published online: 9 DEC 2014 | DOI: 10.1002/ejic.201402764

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      Five new phosphonate-based uranyl–organic hybrids were crystallized in the presence of a variety of alkali and organoammonium cations using hydroxyphosphonate ligands. They represent the first examples of such hybrids constructed in this way. The steric effects from the phenyl ring and the –OH groups of the hydroxyphosphonate moiety play major roles in directing the structure topologies.

  5. Short Communications

    1. Water Oxidation

      Perfluorinated Cobalt Phthalocyanine Effectively Catalyzes Water Electrooxidation

      Natalia Morlanés, Khurram S. Joya, Kazuhiro Takanabe and Valentin Rodionov

      Article first published online: 8 DEC 2014 | DOI: 10.1002/ejic.201403015

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      Water oxidation is efficiently electrocatalyzed by a fluorinated cobalt phthalocyanine (CoFPc) immobilized on fluorine-doped tin oxide surfaces. CoFPc molecular species are revealed as the operational active sites. At 2 V (vs. RHE, pH 7), electrocatalytic water oxidation is sustained for at least 8 h (TON ≈ 1.0 × 105), producing about 4 μmol O2 h–1 cm–2 with no measurable catalyst degradation.

  6. Full Papers

    1. Scorpionand Probes

      Using Click Chemistry to Tune the Properties and the Fluorescence Response Mechanism of Structurally Similar Probes for Metal Ions

      Sandra Ast, Stefanie Kuke, Peter J. Rutledge and Matthew H. Todd

      Article first published online: 5 DEC 2014 | DOI: 10.1002/ejic.201402811

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      In these scorpionand molecular probes, the triazole connectivity, the carbon linker, and the fluorescent tail all combine to modulate photophysical behavior and metal responsiveness.

    2. Alkaline-Earth Coordination Networks

      Alkaline-Earth (Mg–Ba) Coordination Networks Built Around the Tris(dipicolinato)cerate(3) Ion: Highly Hydrated Networks That Survive Dehydration

      S. M. Elahi and M. V. Rajasekharan

      Article first published online: 5 DEC 2014 | DOI: 10.1002/ejic.201402591

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      The CeIII–dipic–AE–H2O system generates microporous coordination networks of various dimensionalities in the Mg–Ba series.

    3. Lead Tellurium Oxides

      Formation and Stability of Gaseous Ternary Oxides of Group 14–16 Elements and Related Oxides of Group 15 Elements: Mass Spectrometric and Quantum Chemical Study

      Katerina Kunkel, Edgar Milke and Michael Binnewies

      Article first published online: 4 DEC 2014 | DOI: 10.1002/ejic.201402734

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      The formation of four hitherto unknown lead tellurium oxides – PbTeO3, PbTe2O5, Pb2TeO4 and Pb2Te2O6 – was observed in the gas phase by means of a mass-spectrometric Knudsen-cell method. The enthalpies of formation for these oxides were obtained experimentally by means of a mass-spectrometric method and confirmed theoretically using quantum chemical calculations.

    4. Curcurbiturils

      Coordination of Alkaline-Earth Metal Ions in Inverted Cucurbit[6]uril Supramolecular Assemblies Formed in the Presence of Tetrachloride Zincates

      De-Qing Zhang, Tao Sun, Yun-Qian Zhang, Sai-Feng Xue, Qian-Jiang Zhu, Jian-Xin Zhang and Zhu Tao

      Article first published online: 3 DEC 2014 | DOI: 10.1002/ejic.201402932

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      Coordination in supramolecular assemblies in aqueous HCl solutions was investigated by reacting alkaline-earth cations and inverted cucurbit[6]uril in the presence of the structure-directing agent, tetrachloride zincate ion.

    5. Fluorescent Probes

      A Simple Fluorescent Probe Derived from Naphthylamine for Selective Detection of HgII, FeII and FeIII Ions in Mixed Aqueous Media: Applications in Living Cells and Logic Gates

      Kaushik Ghosh, Sweety Rathi, Pankaj Gupta, Priya Vashisth and Vikas Pruthi

      Article first published online: 3 DEC 2014 | DOI: 10.1002/ejic.201402910

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      A naphthylamine-based fluorescence probe was used for sensing of HgII, FeII, and FeIII by a chelation-enhanced quenching mechanism and could be utilized for in vivo application and in logic gates.

    6. C–C Activation

      Photochemical Carbon–Carbon Bond Cleavage of CF3-Substituted (dppbe)Pt02-tolane) Complexes

      Sebastian Gröber, Helmar Görls and Wolfgang Weigand

      Article first published online: 3 DEC 2014 | DOI: 10.1002/ejic.201402883

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      (dppbe)Pt(η2-tolane) [dppbe = 1,2-bis(diphenylphosphino)benzene] complexes with CF3 groups at various positions (ortho, meta, and para) of the tolane ligand are synthesized. This type of complex undergoes photochemical carbon–carbon bond cleavage of the C(sp)–C(sp2) atoms in solution and in the solid state. Additionally, this remarkable reaction is reversible under thermal conditions in solution.

    7. Phase Diagrams

      Unexpectedly Complex Crystalline Phases in the MSO3F–Ag(SO3F)2 Phase Diagram (M = Na, K, Rb, Cs)

      T. Michałowski, Z. Mazej, A. Budzianowski, Z. Jagličić, P. J. Leszczyński and W. Grochala

      Article first published online: 2 DEC 2014 | DOI: 10.1002/ejic.201402948

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      The ability of the fluorosulfate anion to form complex paramagnetic salts with alkali metal and AgII cations has been scrutinized. The SO3F anion efficiently transfers magnetic superexchange between AgII centers in complex MAgI2AgII(SO3F)5 antiferromagnets, and the superexchange constant reaches –19.1 meV for the K salt.

    8. Hydrosilylation

      Solvent-Free Hydrosilylation of Terminal Alkynes by Reaction with a Nonclassical Ruthenium Hydride Pincer Complex

      Christopher Conifer, Chidambaram Gunanathan, Torsten Rinesch, Markus Hölscher and Walter Leitner

      Article first published online: 2 DEC 2014 | DOI: 10.1002/ejic.201403016

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      A selective catalyst system for the hydrosilylation of alkyl alkynes under mild, solvent-free conditions has been developed with the ruthenium pincer complex [Ru(tBuPNP)(H2)(H)2] [tBuPNP = 2,6-bis(di-tert-butylphosphinomethyl)pyridine].

    9. Multinuclear Complexes

      Homometallic FeIII4 and Heterometallic {FeIII4LnIII2} (Ln = Dy, Tb) Complexes – Syntheses, Structures, and Magnetic Properties

      Joydeb Goura, Valeriu Mereacre, Ghenadie Novitchi, Annie K. Powell and Vadapalli Chandrasekhar

      Article first published online: 2 DEC 2014 | DOI: 10.1002/ejic.201402636

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      The reactions of the multisite ligand 2-methoxy-6-{[2-(2-hydroxyethylamino) ethylimino]methyl}phenol with Fe(ClO4)2·4H2O or a combination of Fe(ClO4)2·4H2O and Ln(NO3)3·5H2O [DyIII and TbIII] in the presence of Me4NOH and pivalic acid afford a tetranuclear Fe4 complex and hexanuclear FeIII4LnIII2 complexes. Magnetic studies reveal weak antiferromagnetic coupling between the FeIII and LnIII ions.

    10. Graphene Organometallics

      Chromium Tricarbonyl and Chromium Benzene Complexes of Graphene, Their Properties, Stabilities, and Inter-Ring Haptotropic Rearrangements – A DFT Investigation

      Igor P. Gloriozov, Rémi Marchal, Jean-Yves Saillard and Yuri F. Oprunenko

      Article first published online: 2 DEC 2014 | DOI: 10.1002/ejic.201402879

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      DFT calculations show that organometallic moieties such as Cr(CO)3 or Cr(benzene) can move easily on large polyaromatic hydrocarbons.

    11. ULTTC Material

      Structure and Microwave Dielectric Properties of Ultralow-Temperature Cofirable BaV2O6 Ceramics

      Unnimaya Avanoor Neelakantan, Suresh Elattuvalappil Kalathil and Ravendran Ratheesh

      Article first published online: 28 NOV 2014 | DOI: 10.1002/ejic.201402844

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      Ceramics that can be sintered at temperatures lower than the melting point of aluminum (660 °C) are classified as ULTTC ceramics. In the present work, a BaV2O6 microwave ceramic suitable for ULTCC applications was sintered at 550 °C, and phase formation was confirmed by DSC/TGA, X-ray diffraction, and Raman spectroscopic studies. The sintered ceramic has excellent compatibility with Al electrodes.

    12. Ferrocene Bioconjugates

      Synthesis and Conformational Study of Bioconjugates Derived from 1-Acetyl-1′-aminoferrocene and α-Amino Acids

      Mojca Čakić Semenčić, Veronika Kovač, Ivan Kodrin, Lidija Barišić and Vladimir Rapić

      Article first published online: 27 NOV 2014 | DOI: 10.1002/ejic.201402837

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      Conformational analysis (IR, NMR,CD and DFT) revealed that nonsymmetric bioorganometallics [Boc-AA-NH-Fn-COMe; Boc = tert-butoxycarbonyl; AA = Gly, L-Ala, L-Val; Fn = 1,1′-ferrocenylene] adopt helically ordered conformations supported by intramolecular hydrogen bonds.

    13. Diphosphine Ligands

      Substitutional Lability of Diphosphine Ligands in Tetrahedral Iron(II) Chloro Complexes

      Robert Langer, Friedrich Bönisch, Leon Maser, Clemens Pietzonka, Lisa Vondung and Thomas Philipp Zimmermann

      Article first published online: 27 NOV 2014 | DOI: 10.1002/ejic.201402859

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      The synthesis and reactivity of iron diphosphine complexes towards chelating amines is described. The results illustrate the fundamental difference with respect to the corresponding ruthenium complexes and demonstrate that the investigated diphosphine ligands are bound too weakly in iron(II) complexes to be used for active iron-based catalysts.

    14. Siloxanes

      An Efficient Catalytic Approach for the Synthesis of Unsymmetrical Siloxanes

      Grzegorz Hreczycho

      Article first published online: 27 NOV 2014 | DOI: 10.1002/ejic.201402904

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      An efficient methodology for the synthesis of unsymmetrical disiloxanes by means of catalytic one-pot hydrolysis/O-silylation of alkoxysilanes with allylsilanes (via silanol intermediates) in the presence of scandium(III) trifluoromethanesulfonate under mild conditions is described. Unsaturated siloxane products are used as substrates for further functionalization through the catalytic hydrosilylation reaction.

  7. Short Communications

    1. Zirconacyclopentadienes

      Cyclizations of 1,2-Bis(pinacolylboryl)acetylene at Zirconocene

      Kai Altenburger, Perdita Arndt, Anke Spannenberg and Uwe Rosenthal

      Article first published online: 27 NOV 2014 | DOI: 10.1002/ejic.201402941

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      In the reaction of [Cp2Zr] with 1,2-bis(pinacolylboryl)acetylene, zirconacyclopentadiene 4 was obtained. It reacts with (Ph3P)2NiCl2 and 3-hexyne to give the hexasubstituted benzene, 1,2-ethyl-3,4,5,6-pinacolylborylbenzene (6), and a heterometallic ferrol-type complex 7. The formation of 7 is the inhibition process for the synthesis of 6.

  8. Full Papers

    1. Layered Compounds

      The Synthesis, Structure, and Electrical Characterization of (SnSe)1.2TiSe2

      Devin R. Merrill, Daniel B. Moore, Jeffrey Ditto, Duncan R. Sutherland, Matthias Falmbigl, Markus Winkler, Hans-Fridtjof Pernau and David C. Johnson

      Article first published online: 27 NOV 2014 | DOI: 10.1002/ejic.201402814

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      The first intergrowth compound in the Sn–Ti–Se system was synthesized from modulated elemental reactants and was found to have a large negative Seebeck coefficient for 1021 carriers. Electrical characterization suggests that charge transfer occurs between layers to stabilize the superstructure and provides conducting electrons to the TiSe2 layer.

    2. Magnetic Properties

      Unexpected Strong Antiferromagnetic Interaction in [CuCyclam][Ni(1,2-benzenedithiolate)2]2

      Junichi Nishijo, Kazuya Iwama and Masaya Enomoto

      Article first published online: 27 NOV 2014 | DOI: 10.1002/ejic.201402818

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      New molecule-based magnetic materials containing quasiplanar [CuCyclam]2+ cations and planar [Ni(bdt)2] anions (bdt = 1,2-benzenedithiolate) are prepared. Magnetic measurements reveal the existence of a rather strong exchange interaction of 2J/kB = –66 K, which is caused by the face-to-face stacking of the planar molecules in [CuCyclam][Ni(bdt)2]2.

    3. Ionic Liquids

      Understanding the Dynamics of Eu3+ Ions in Room-Temperature Ionic Liquids – Electrochemical and Time-Resolved Fluorescence Spectroscopy Studies

      Ruma Gupta, Santosh K. Gupta, J. S. Gamre, K. V. Lohithakshan, V. Natarajan and S. K. Aggarwal

      Article first published online: 27 NOV 2014 | DOI: 10.1002/ejic.201402713

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      The present work deals with the extraction of Eu3+ ions (as a surrogate for Am3+ ions) from acidic feed solutions with dihexyl N,N-diethylcarbamoylmethylphosphonate (DHDECMP) in the ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][NTf2]). The electrochemical and spectroscopic properties of Eu3+–DHDECMP in [bmim][NTf2] are investigated.

    4. Hybrid Polymer Films

      Photoactive Hybrid Polymer Films Incorporated with Lanthanide Complexes and ZIF-8 for Selectively Excited Multicolored Luminescence

      Chang Liu and Bing Yan

      Article first published online: 26 NOV 2014 | DOI: 10.1002/ejic.201402979

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      A series of photoactive polymer hybrid films fabricated with both Ln complexes and ZIF-8 is described. The films show discrete luminescence from ZIF-8 and the Ln complexes, and there is no energy coupling between the two emissive centers. By selective excitation with different wavelengths, the luminescence can be tuned from blue (ZIF-8) to red (Eu3+), green (Tb3+) or yellow (Eu3+/Tb3+) and even white by integrating the emission of both Eu3+ and the polymer unit.

    5. Silsesquioxanes

      Cinnamate-Functionalized Cage Silsesquioxanes as Photoreactive Nanobuilding Blocks

      Wenyan Yang, Yanchang Gan, Xuesong Jiang and Hongzhi Liu

      Article first published online: 26 NOV 2014 | DOI: 10.1002/ejic.201402920

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      From potassium cinnamate, photoreactive mono-, octa-, and deca(propyl cinnamate)-functionalized cage silsesquioxanes are synthesized by simple nucleophilic substitution reactions with chloropropyl-substituted octasilsesquioxanes. Among them, octa(propyl cinnamate)silsesquioxane exhibits excellent properties such as high photopolymerization conversion of double bonds and thermal stability.

  9. Microreviews

    1. Ionogels

      Electrospinning of Ionogels: Current Status and Future Perspectives

      Andreas Taubert

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

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

  10. Full Papers

    1. Cytotoxic Organoplatinum Complexes

      Platinum Diolefin Complexes – Synthesis, Structures, and Cytotoxicity

      Anna Lüning, Michael Neugebauer, Verena Lingen, Alexander Krest, Kathrin Stirnat, Glen B. Deacon, Penny R. Drago, Ingo Ott, Julia Schur, Ingo Pantenburg, Gerd Meyer and Axel Klein

      Article first published online: 24 NOV 2014 | DOI: 10.1002/ejic.201402954

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      Organometallic diolefin platinum(II) complexes [(∥∥)PtCl2], [(∥∥)Pt(R)(L)] and [(∥∥)Pt(R)2] are synthesised and characterised. Cytotoxicity experiments (HT-29 and MCF-7 cancer cell lines) show that the introduction of labile diolefin ligands ∥∥ or labile coligands does not lead to increased cytotoxicity compared with that of the established 1,5-cyclooctadiene derivatives.

  11. Short Communications

    1. Dynamics of Pd Complexes

      Synthesis and Characterization of ortho-Thio-Functionalized Triarylmethyl Palladium Complexes

      Stephan Schöler, Klaus Merz, Arik Puls, Manuela Winter and Gerald Dyker

      Article first published online: 21 NOV 2014 | DOI: 10.1002/ejic.201402908

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      Various inter- and intramolecular binding modes between palladium salts and ortho-thio-substituted triarylmethyl ligands are detected in the solid state. The corresponding dynamic behavior in solution is studied by temperature-dependent NMR spectroscopy.

  12. Full Papers

    1. Two-Photon Absorption

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

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

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

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

    2. Imaging Agents

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

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

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

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

    3. Lanthanide Nitride Bismuthides

      Lanthanide(III) Nitride Bismuthides M2NBi (M = La–Nd) and Their Potential as Topological Insulators

      Klaus K. Wolff, Falk Lissner, Jürgen Köhler and Thomas Schleid

      Article first published online: 17 NOV 2014 | DOI: 10.1002/ejic.201402733

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      Four lanthanide(III) nitride bismuthides of the class M2NBi (M = La–Nd) were synthesized and characterized by X-ray diffraction. All four compounds crystallize tetragonally in the space group P4/nmm and anti-isotypically with KCoO2 or BaNiS2. The partial density of states and the band structure of La2NBi show that this compound has to be considered a zero-band-gap semiconductor.

    4. Crystal Nucleation

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

      Markus Walther and Dirk Zahn

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

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

  13. Microreviews

    1. Host–Guest Chemistry

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

      Makoto Ogawa, Kanji Saito and Minoru Sohmiya

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

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

  14. Full Papers

    1. Polyurethane Nanocomposites

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

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

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

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

    2. Electrolytes

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

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

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

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

    3. Dioxygen Activation

      Mechanistic Insights into Phenol Oxidation by a Copper(II) Complex of a Pyridine- and Amide-Containing Copolymer in an Aqueous Medium

      Vasiliki Lykourinou and Li-June Ming

      Article first published online: 7 NOV 2014 | DOI: 10.1002/ejic.201402778

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      A CuII complex of a pyridine- and amide-containing copolymer catalyzes phenol hydroxylation/oxidation in aqueous methanol at pH 8.0 and 25 °C. First-order rate accelerations by factors of 4.2 × 105 and 1.4 × 105 and deuterium kinetic isotope effects of 2.8 and 1.2, respectively, were observed with and without H2O2. The results suggest that different mechanisms apply for oxidation by O2 and H2O2.

    4. Cluster Compounds

      Hydrolytic Stability and Hydrogen Peroxide Activation of Zirconium-Based Oxoclusters

      Francesco Faccioli, Matthias Bauer, Danilo Pedron, Antonio Sorarù, Mauro Carraro and Silvia Gross

      Article first published online: 6 NOV 2014 | DOI: 10.1002/ejic.201402767

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      The hydrolytic stability and reactivity of Zr6 and Zr12 oxoclusters are investigated by FTIR, Raman, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The clusters are stable in water at neutral pH, and peroxo complexes are detected in the presence of hydrogen peroxide. A kinetic study highlights the catalytic potential of the clusters for the oxidation of methyl p-tolyl sulfide.

    5. Water Splitting

      Synthetic Strategies for Variably Substituted Ruthenium–Imidazophenanthrolinium Complexes

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

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

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

    6. Heterobimetallic Complexes

      Lithium Complexes of Asymmetric Hydrogen Tetraimido Sulfate

      Julia Matussek, Regine Herbst-Irmer and Dietmar Stalke

      Article first published online: 15 OCT 2014 | DOI: 10.1002/ejic.201402624

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      Asymmetrically substituted hydrogen tetraimido sulfate ligands provide two opportunities to generate metal complexes. Firstly, the lithium metal can be exchanged in a transmetalation reaction, and secondly, the proton can be replaced by an additional substituent or another metal. This gives access to heterobimetallic complexes.

  15. Microreviews

    1. Carbon Materials

      Ionic Liquid Based Approaches to Carbon Materials Synthesis

      Zai-Lai Xie and Dang Sheng Su

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

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

  16. Full Papers

    1. Nanocomposite Films

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

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

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

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

    2. Layered Compounds

      Nanostructuring of Bridged Organosilane Precursors with Pendant Alkyl Chains

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

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

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

  17. Microreviews

    1. Supramolecular Chemistry

      Constitutional Hybrid Materials – Toward Selection of Functions

      Mihail Barboiu

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

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

  18. Full Papers

    1. Conformation Studies

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

      Anna Martinelli

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

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

    2. Ionic Liquids

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

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

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

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

    3. Polymorphs

      Prospective Electroluminescent Hybrid Materials

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

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

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

    4. Surface Functionalization

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

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

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

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

    5. Self-Healing Materials

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

      Tom Engel and Guido Kickelbick

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

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

    6. Coordination Polymers

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

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

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

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

    7. Luminescence

      Modelling the Luminescence of Phosphonate Lanthanide–Organic Frameworks

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

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

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

    8. Gas Adsorbing Materials

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

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

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

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

    9. Biosensing

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

      Katarzyna Grochowska, Katarzyna Siuzdak and Gerard Śliwiński

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

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

    10. Composite Structures

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

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

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

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

    11. Selective Crystallization

      Sulfonated Polymethylsiloxane as an Additive for Selective Calcium Oxalate Crystallization

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

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

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

    12. Nickel Nanoparticles

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

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

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

      Thumbnail image of graphical abstract

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

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