European Journal of Inorganic Chemistry

Cover image for Vol. 2014 Issue 21

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

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 3.12

ISI Journal Citation Reports © Ranking: 2012: 11/44 (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. Short Communications

    1. Field-Effect Transistors

      Asymmetric Phase Transitions Observed at the Interface of a Field-Effect Transistor Based on an Organic Mott Insulator

      Hiroshi M. Yamamoto, Yoshitaka Kawasugi, Hengbo Cui, Masaki Nakano, Yoshihiro Iwasa and Reizo Kato

      Article first published online: 6 MAY 2014 | DOI: 10.1002/ejic.201402025

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      An ambipolar field-effect transistor is fabricated with an organic Mott insulator as a channel material. It shows Mott transitions both in the n-type and p-type regions, which merge at lower temperatures. These transitions are asymmetric at the polarity inversion, and they show a difference between hole doping and electron doping into an organic Mott insulator.

  2. Full Papers

    1. Crystal Engineering

      Reversible Solvent-Exchange-Driven Transformations in Multifunctional Coordination Polymers Based on Copper-Containing Organosulfur Ligands

      Almudena Gallego, Oscar Castillo, Carlos J. Gómez-García, Félix Zamora and Salome Delgado

      Article first published online: 6 MAY 2014 | DOI: 10.1002/ejic.201400085

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      Direct synthesis of a series of coordination polymers based on copper with chloride or bromide and dipyrimidinedisulfide, leads to a structural variety of coordination polymers. The products show crystal-to-crystal transformations and multifunctional electronic properties including semiconductivity, magnetism, and NIR fluorescence.

  3. Microreviews

    1. Organic Conductors

      Dual-Layered Quasi-Two-Dimensional Organic Conductors with Presumable Incoherent Electron Transport

      Rimma Lyubovskaya, Elena Zhilyaeva, Gena Shilov, Alain Audouard, David Vignolles, Enric Canadell, Sergei Pesotskii and Rustem Lyubovskii

      Article first published online: 28 APR 2014 | DOI: 10.1002/ejic.201402041

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      The main peculiarities of dual-layered conductors (D)4MBr4(C6H6–nXn) are their alternating different conducting layers, structural phase transitions, and different types of conductivity, metallic along and semiconducting across the conducting layers. The Fermi surface of this compound provides a roadmap for interpreting the transport properties of quasi-two-dimensional organic conductors.

  4. Full Papers

    1. Functional Materials

      Structural and Physical Properties of (EDO-TTF-Cl)2XF6 (X = As, Sb): Geometrical Aspects for Monosubstituted EDO-TTF (EDO-TTF = 4,5-ethylenedioxytetrathiafulvalene)

      Manabu Ishikawa, Yoshiaki Nakano, Mikio Uruichi, Akihiro Otsuka, Kyuya Yakushi and Hideki Yamochi

      Article first published online: 24 APR 2014 | DOI: 10.1002/ejic.201400128

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      The semiconducting and metallic compounds (EDO-TTF-Cl)2XF6 (X = As and Sb, respectively) were obtained. Their properties are well correlated with their degree of intracolumnar dimerization. The in-plane intermolecular displacements in the stacking columns are the key parameters to understand the chemical pressure.

    2. Paramagnetic Molecular Metals

      Metallic Charge-Transfer Salts of Bis(ethylenedithio)tetrathiafulvalene with Paramagnetic Tetrachloro(oxalato)rhenate(IV) and Tris(chloranilato)ferrate(III) Anions

      Samia Benmansour, Eugenio Coronado, Carlos Giménez-Saiz, Carlos J. Gómez-García and Carola Rößer

      Article first published online: 17 APR 2014 | DOI: 10.1002/ejic.201402023

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      Three new paramagnetic molecular conductors have been prepared with the magnetic anions [ReCl4(C2O4)]2– and [Fe(C6O4Cl2)3]3–. ET[ReCl4(C2O4)] [ET = bis(ethylenedithio)tetrathiafulvalene] is a semiconductor that contains ET2+ dications. ET4[ReCl4(C2O4)] is metallic down to 110 K. ET6[Fe(C6O4Cl2)3] has high conductivity and is the first radical salt with a tris(anilato)metalate anion.

    3. Molecular Conductors

      Enantiopure Conducting Salts of Dimethylbis(ethylenedithio)tetrathiafulvalene (DM-BEDT-TTF) with the Hexachlororhenate(IV) Anion

      Flavia Pop, Magali Allain, Pascale Auban-Senzier, José Martínez-Lillo, Francesc Lloret, Miguel Julve, Enric Canadell and Narcis Avarvari

      Article first published online: 14 APR 2014 | DOI: 10.1002/ejic.201400125

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      Two enantiomerically pure radical cation salts based on the (S,S)- and (R,R)-dimethylbis(ethylenedithio)tetrathiafulvalene (DM-BEDT-TTF) donor and the paramagnetic [ReCl6]2– dianion show semiconducting behaviour.

    4. Electron Correlation

      Molecular Conductors with Effectively Half-Filled Electronic States Based on Tetrathiafulvalene Derivatives Condensed with a 2-Isopropylidene-1,3-dithiole Ring

      Keisuke Furuta, Shuhei Kohno, Takashi Shirahata and Yohji Misaki

      Article first published online: 10 APR 2014 | DOI: 10.1002/ejic.201402006

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      Molecular conductors (3)2[M(CN)2] (M = Ag and Au) have been successfully prepared and their physical properties and structures have been investigated. The electronic nature of these salts is the effectively half-filled electronic state. (3)2[Au(CN)2] shows nonmetallic behavior below 50 K. These results suggest that the present salts lie on the border between the metallic and insulating phases.

    5. Ligand Design

      Tetrathiafulvalene-Based Phenanthroline Ligands: Synthesis, Crystal Structures, and Electronic Properties

      Esmah Belhadj, Abdelkrim El-Ghayoury, Thomas Cauchy, Magali Allain, Miloud Mazari and Marc Sallé

      Article first published online: 9 APR 2014 | DOI: 10.1002/ejic.201402073

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      Three redox-active phenanthroline–tetrathiafulvalene ligands incorporating different linkers between the accepting and the donating subunits have been synthesized. The critical effect of the linker on the intramolecular charge transfer between both parts is experimentally and theoretically studied.

    6. Radical Cation Salts

      Metallic Bi- and Monolayered Radical Cation Salts Based on Bis(ethylenedithio)­tetrathiafulvalene (BEDT-TTF) with the Tris(oxalato)gallate Anion

      Tatiana G. Prokhorova, Lev I. Buravov, Eduard B. Yagubskii, Leokadiya V. Zorina, Sergey V. Simonov, Rimma P. Shibaeva and Vladimir N. Zverev

      Article first published online: 9 APR 2014 | DOI: 10.1002/ejic.201400132

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      Bilayered and monolayered metallic radical cation salts based on bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with the [GaIII(C2O4)3]3–· anion have been prepared and investigated. Metallic α and nonmetallic “pseudo-κ” layers of BEDT-TTF alternate in the structure of the bilayered salt, whereas the conducting layers in the monolayered salt have only metallic β″-type packing.

    7. Crystal Engineering

      Mixed-Valence Biferrocenium Salts of Xn–TCNQ (X = F, Cl; n = 1, 2): Correlation between Molecular Structures and Assembled Structures

      Tomoyuki Mochida, Yusuke Funasako, Shizue Yamazaki and Hatsumi Mori

      Article first published online: 9 APR 2014 | DOI: 10.1002/ejic.201400093

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      Biferrocenium salts with Xn–TCNQ (X = F, Cl; n = 1, 2) exhibit a 1:2 D/A ratio, consisting of mixed-valence cations and anions containing acceptor dimers. These salts exhibit segregated-stack structures, mixed-stack structures, and intermediate structures depending on the donor substituents.

    8. Lanthanides

      Magnetic Studies of Redox-Active Tetrathiafulvalene-Based Complexes: Dysprosium vs. Ytterbium Analogues

      Julie Jung, Tamyris T. da Cunha, Boris Le Guennic, Fabrice Pointillart, Cynthia L. M. Pereira, Javier Luzon, Stéphane Golhen, Olivier Cador, Olivier Maury and Lahcène Ouahab

      Article first published online: 21 MAR 2014 | DOI: 10.1002/ejic.201400121

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      The crystal-field energy splitting of the ground-state multiplets of the complexes Dy and Yb was evaluated, and they demonstrate Ising and non-Ising character. Both anisotropy axis directions for the MJ ground states were determined in agreement with the oblate and prolate electronic distribution for DyIII and YbIII ions. This results in SMM and non-SMM behaviour for Dy and Yb, respectively.

    9. Isotropic 3D π-Conductors

      Isotropic Three-Dimensional Molec­ular Conductor Based on the Coronene Radical Cation

      Yukihiro Yoshida, Mitsuhiko Maesato, Yoshihide Kumagai, Motohiro Mizuno, Kazuhide Isomura, Hideo Kishida, Masanari Izumi, Yoshihiro Kubozono, Akihiro Otsuka, Hideki Yamochi, Gunzi Saito, Kaplan Kirakci, Stéphane Cordier and Christiane Perrin

      Article first published online: 20 MAR 2014 | DOI: 10.1002/ejic.201400119

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      The first coronene cation radical salt was electrochemically obtained by combining coronene with a highly-symmetric Mo6Cl142– cluster unit. The salt has a cubic structure with Pmequation imagem symmetry, and merohedrally disordered coronenes undergo an in-plane flipping rotation. The randomly charge-disproportionated coronenes form an isotropic three-dimensional π-conducting network.

    10. Bioorganometallic Complexes

      Self-Assembly Properties of NCN Pincer Palladium(II) Complexes Bearing a Uracil Moiety

      Toshiyuki Moriuchi, Ryohei Ohata, Yuki Sakamoto and Toshikazu Hirao

      Article first published online: 20 MAR 2014 | DOI: 10.1002/ejic.201400131

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      Bioorganometallic compounds were designed by the combination of NCN pincer complexes with a uracil moiety to form intermolecular hydrogen-bonded assemblies, wherein the hydrogen-bonding patterns were found to depend on the ancillary ligands.

    11. Photoresponsive Conductors

      Photofunctional Conductors Based on TTF-BODIPY Dyads Bearing p-Phenylene and p-Phenylenevinylene Spacers

      Keijiro Tsujimoto, Reiko Ogasawara, Takahiro Nakagawa and Hideki Fujiwara

      Article first published online: 17 MAR 2014 | DOI: 10.1002/ejic.201400103

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      New D–A-type TTF-BODIPY dyads (TTF = tetrathiafulvalene and BODIPY = 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) with a p-phenylene or p-phenylenevinylene spacer have been synthesized. These dyads exhibit photoresponsive conducting properties such as photoelectric conversion functionality in thin-film samples and photoinduced conductivity in their single-crystal samples.

  5. Short Communications

    1. Molecular Metals

      Pressure-Induced Metallic Conductivity in the Single-Component Molecular Crystal [Ni(dmit)2]

      Hengbo Cui, Takao Tsumuraya, Tsuyoshi Miyazaki, Yoshinori Okano and Reizo Kato

      Article first published online: 6 MAR 2014 | DOI: 10.1002/ejic.201400130

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      Four-probe electrical resistivity measurements on the single-component molecular crystal [Ni(dmit)2] (dmit = 1,3-dithiole-2-thione-4,5-dithiolate) up to 25.5 GPa by using a diamond anvil cell (DAC) technique with high-quality hydrostatic conditions reveal a metallic state above 15.9 GPa. Ab initio DFT calculations and tight-binding band calculations indicate a 3D Fermi surface under high pressure, which explains the metallic state.

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