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. 1 - 100
  2. 101 - 105
  1. Full Papers

    1. Silver Clusters

      Synthesis of Atomically Precise Silver Clusters by Using the Miscibility Principle

      Atanu Ghosh and Thalappil Pradeep

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

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

    2. Blue Emitters

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

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

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

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

    3. Lewis Acids

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

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

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

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

    4. Bridged Complexes

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

      Kathi Carl, Anke Sterzik, Helmar Görls and Wolfgang Imhof

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

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

    5. Cluster Compounds

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

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

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

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

    6. Solar Cells

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

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

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

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

  2. Short Communications

    1. Inclusion Compounds

      Inclusion of an Iodine Molecule in a Tiara-Like Octanuclear Palladium Thiolate Complex

      Yukari Yamashina, Yasutaka Kataoka and Yasuyuki Ura

      Article first published online: 23 JUL 2014 | DOI: 10.1002/ejic.201402616

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      An iodine molecule is successfully inserted into the inner cavity of a tiara-like octanuclear palladium thiolate complex, [Pd(μ-SCH2CO2Me)2]8. The included iodine molecule coordinates weakly to six palladium atoms in both linear and bent modes. The inclusion complex reacts with an excess amount of I2 to produce a disulfide, which is accompanied by decomposition of the tiara ring.

  3. Full Papers

    1. Photoluminescence

      Photoluminescence of Zinc Complexes: Easily Tunable Optical Properties by Variation of the Bridge Between the Imido Groups of Schiff Base Ligands

      Frédéric Dumur, Emmanuel Contal, Guillaume Wantz and Didier Gigmes

      Article first published online: 23 JUL 2014 | DOI: 10.1002/ejic.201402422

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      Forty Schiff base zinc(II) complexes have been designed and studied for their photoluminescence properties. Interestingly, the nature of the diamine spacer in the ligand is the unique factor that influences the optical properties of the complexes.

    2. Molecular Spintronics

      X-ray Crystallographic Analysis of a Tailor-Made Bis(phthalocyaninato)-TbIII Single-Molecule Magnet as a Fundamental Unit for Supramolecular Spintronic Devices

      Svetlana Klyatskaya, Andreas Eichhöfer and Wolfgang Wernsdorfer

      Article first published online: 23 JUL 2014 | DOI: 10.1002/ejic.201402421

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      The structure of a [Pc–Tb–Pc*] SMM was determined. A single-crystal X-ray diffraction analysis revealed an effective intermolecular π–π interaction leading to the formation of π dimers, which are stacked with neighboring dimers in parallel columns with an axis tilted by 30° with respect to the C4 axis of individual molecules. Isostructural Dy and Ho analogues were synthesized and characterized.

    3. Pd–Ni Bimetals

      Compositionally Controlled Self-Assembly of Hierarchical Pd–Ni Bimetallic Chains

      Peiyu Jin, Xin Liang, Yeheng He, Sijia Liu and Xiaolin Zhu

      Article first published online: 23 JUL 2014 | DOI: 10.1002/ejic.201402173

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      The self-assembly of Pd–Ni bimetals with various compositions was performed by a one-pot reaction. The formation mechanism for these assemblies is proposed, in which the self-assembly behaviours were controlled by the competition between the surfactant interaction and the magnetic dipole interaction. The catalytic performance of these Pd–Ni assemblies is strongly dependent on their compositions.

    4. Metallocenes

      Synthesis and Molecular Structures of Monosubstituted Pentamethylcobaltocenium Cations

      Anne Wolter-Steingrube, Bernhard E. C. Bugenhagen, Carmen Herrmann and Jürgen Heck

      Article first published online: 22 JUL 2014 | DOI: 10.1002/ejic.201402443

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      From the zwitterion 1, the aminocobaltocenium cation 6+ can be synthesized in five steps. The target compound 6+ demonstrates an electronic structure between that of an amine and that of an iminium cation. It reacts as a weak acid in aqueous solution and can be oxidized to the corresponding nitrocobaltocenium cation 7+ like primary amines.

    5. Nanostructures

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

      Santu Das, Preethi Thomas and Soumyajit Roy

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

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

    6. Actinide Complexes

      Mixed-Donor Amido–Siloxo Actinide(IV) Halide and Alkyl Complexes with an Aryl Cipso Interaction

      Cassandra E. Hayes, Dayle E. Gill, Matthew L. Brown and Daniel B. Leznoff

      Article first published online: 22 JUL 2014 | DOI: 10.1002/ejic.201402226

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      A new series of mixed-donor amido–siloxo actinide(IV) halide and alkyl complexes feature an aryl Cipso interaction of the amido aryl group with the metal centre.

  4. Microreviews

    1. Phenacene Field-Effect Transistors

      Transistor Application of Phenacene Molecules and Their Characteristics

      Yoshihiro Kubozono, Xuexia He, Shino Hamao, Kazuya Teranishi, Hidenori Goto, Ritsuko Eguchi, Takashi Kambe, Shin Gohda and Yasushi Nishihara

      Article first published online: 22 JUL 2014 | DOI: 10.1002/ejic.201402168

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      Field-effect transistors (FETs) can be fabricated with thin films and single crystals of phenacene. The excellent p-channel FET characteristics that have been found by our group are fully reported in this review.

  5. Full Papers

    1. Reaction Mechanisms

      Kinetics and Mechanism of the Reaction of Hydrogen Sulfide with Diaquacobinamide in Aqueous Solution

      Denis S. Salnikov, Sergei V. Makarov, Rudi van Eldik, Polina N. Kucherenko and Gerry R. Boss

      Article first published online: 21 JUL 2014 | DOI: 10.1002/ejic.201402082

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      The reduction of diaquacobinamide [(H2O)2Cbi(III)] by hydrogen sulfide proceeds through inner-sphere electron transfer (ISET) in the two complexes with one coordinated HSligand, viz., (HO)(HS)Cbi(III) and (H2O)(HS)Cbi(III), to form the reduced cobinamide complex [(H)S]Cbi(II). ISET does not proceed in the (HS)2Cbi(III) complex.

    2. Environmental Chemistry

      Aerial CO2 Trapped as CO32– Ions in a Dimeric Capsule That Efficiently Extracts Chromate, Sulfate, and Thiosulfate from Water by Anion-Exchange Metathesis

      Ranjan Dutta, Sourav Chakraborty, Purnandhu Bose and Pradyut Ghosh

      Article first published online: 21 JUL 2014 | DOI: 10.1002/ejic.201402139

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      In the solid state, a tripodal urea receptor encapsulates CO32– ions in its dimeric capsular assembly, which is further exploited for the liquid–liquid (L–L) extraction of CrO42–, S2O32–, and SO42– ions from water. Different spectroscopic techniques and X-ray diffraction studies confirm the efficient extraction of these environmentally relevant anions.

    3. Lanthanide Complexes

      Tetranuclear [2×2] Square-Grid Lanthanide(III) Complexes: Syntheses, Structures, and Magnetic Properties

      Sourav Biswas, Sourav Das, Jan van Leusen, Paul Kögerler and Vadapalli Chandrasekhar

      Article first published online: 21 JUL 2014 | DOI: 10.1002/ejic.201402326

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      The reactions of a multicompartmental ligand with rare-earth(III) nitrate salts afford a series of homometallic Ln4 complexes [Ln = Dy, Tb, Gd, and Er] with [2×2] square-grid topology. Magnetic studies reveal the presence of all-antiferromagnetic exchange interactions and ligand-field-induced effects for the Dy, Tb, and Er complexes, whereas an isotropic model suffices for the Gd complex.

    4. Copper Catalysts

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

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

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

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

    5. Cross-Coupling

      Hydrophilic Pd0 Complexes Based on Sugars for Efficient Suzuki–Miyaura Coupling in Aqueous Systems

      Giulia Tarantino, Massimiliano Curcio, Andrea Pica, Andrea Carpentieri, Maria E. Cucciolito, Francesco Ruffo, Aldo Vitagliano and Matteo Lega

      Article first published online: 21 JUL 2014 | DOI: 10.1002/ejic.201402456

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      Sugar-derived hydrophilic Pd0 complexes are prepared and tested in aqueous Suzuki–Miyaura cross-coupling reactions. These conditions allow the green and sustainable synthesis of biaryls. The best catalysts achieve very good performances [turnover frequencies (TOFs) up to 3.5 × 104 h–1; catalyst loadings down to 0.0010 mol-%], among the best reported for this reaction in aqueous conditions.

    6. Ru-Porphyrin Pacman Compound

      High-Yielding Synthesis of a Hetero-Pacman Compound and the Characterization of Intermediates and Side-Products

      Matthias Schwalbe, Pierre Wrzolek, Garima Lal and Beatrice Braun

      Article first published online: 21 JUL 2014 | DOI: 10.1002/ejic.201402459

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      A new high-yielding synthesis towards xanthene-porphyrin precursors is presented. These building blocks can be used for the formation of a multitude of different heterodinuclear complexes with the Pacman architecture. A hetero-Pacman scaffold featuring a porphyrin and a ruthenium polypyridine complex fragment that shows intriguing structural and spectroscopic properties was produced herein by a double Suzuki reaction.

  6. Microreviews

    1. Silver(I) Cyanoximates

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

      Nikolay Gerasimchuk

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

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

    2. Heterometallic Complexes

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

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

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

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

  7. Full Papers

    1. Bismuth Oxido Clusters

      Salicylate-Functionalized Bismuth Oxido Clusters: Hydrolysis Processes and Microbiological Activity

      Maik Schlesinger, Amita Pathak, Sebastian Richter, Dominik Sattler, Andreas Seifert, Tobias Rüffer, Philip C. Andrews, Christoph A. Schalley, Heinrich Lang and Michael Mehring

      Article first published online: 18 JUL 2014 | DOI: 10.1002/ejic.201402493

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      Hydrolysis of either Bi(HSal4Me)3 or [Bi22O26(HSal4Me)14] in dmso gave the 4-methylsalicylate-substituted bismuth oxido cluster [Bi38O45(HSal4Me)24(dmso)14(H2O)2]·4H2O. 1H DOSY NMR and ESI-FTICR MS revealed an on-going growth process to finally give the large cluster. Microbiological activity tests against three strains of H. pylori showed higher activity for smaller bismuth species.

    2. C–S Activation

      Diiron Azamonothiolates by the Scission of Dithiadiazacyclooctanes by Iron Carbonyls

      Tai Lin, Olbelina A. Ulloa, Thomas B. Rauchfuss and Danielle L. Gray

      Article first published online: 18 JUL 2014 | DOI: 10.1002/ejic.201402413

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      It has long been known that Fe0 reagents activate many organosulfur compounds by scission of C–S bonds. Here, we report that S2N2 heterocycles undergo smooth activation by [Fe3(CO)12] to give azamonothiolates, not the well precedented azadithiolates. In these azathiolate complexes, all six CO ligands are diastereotopic.

    3. Luminescent Platinum Complexes

      Phosphorescent PtII Systems Featuring Both 2,2′-Dipyridylamine and 1,3,5-Triazapentadiene Ligands

      Ivan I. Eliseev, Pavel V. Gushchin, Yi-An Chen, Pi-Tai Chou, Matti Haukka, Galina L. Starova and Vadim Yu. Kukushkin

      Article first published online: 18 JUL 2014 | DOI: 10.1002/ejic.201402364

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      The interplay between N,N′-diphenylguanidine and cis-(dpa)(RCN)2PtII species (dpa = 2,2′-dipyridylamine) gives both the so-called tailoring products and the addition products. The latter exhibit intense luminescence in the solid state.

    4. Cluster Compounds

      Homoleptic Molybdenum Cluster Sulfides Functionalized with Noninnocent Diimine Ligands: Synthesis, Structure, and Redox Behavior

      Artem L. Gushchin, Yuliya A. Laricheva, Pavel A. Abramov, Alexander V. Virovets, Cristian Vicent, Maxim N. Sokolov and Rosa Llusar

      Article first published online: 18 JUL 2014 | DOI: 10.1002/ejic.201402343

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      An Mo3S4 cluster coordinated by thiourea ligands is a new precursor in the chemistry of Mo3S4 clusters. Its potential as a convenient starting material has been demonstrated by reactions with 2,2-bipyridine and 1,10-phenanthroline to afford new diimino cluster complexes. The Mo3S4 cluster bearing 1,10-phenanthroline undergoes a reversible two-electron reduction that is phen-centered with strong delocalization on the metal.

    5. Tridentate Ligand Platform

      Neutral and Cationic Alkyl and Amido Group 3 Metal Complexes of Amidine-Amidopyridinate Ligands: Synthesis, Structure, and Polymerization Catalytic Activity

      Vasily Rad'kov, Thierry Roisnel, Alexander Trifonov, Jean-François Carpentier and Evgeny Kirillov

      Article first published online: 17 JUL 2014 | DOI: 10.1002/ejic.201402362

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      New dialkyl, diamido, and cationic amido group 3 metal complexes of amidine-amidopyridine ligands, some featuring β-Si–H···Ln agostic interactions, evidenced in the solid state and by 29Si NMR spectroscopy, have been prepared and used in the polymerization of isoprene and ring-opening polymerization of racemic lactide.

    6. Cluster Compounds

      The Chemistry of Ni–Sb Carbonyl Clusters – Synthesis and Characterization of the [Ni19Sb4(CO)26]4– Tetraanion and the Viologen Salts of [Ni13Sb2(CO)24]n– Carbonyl Clusters

      Cristina Femoni, Maria Carmela Iapalucci, Giuliano Longoni, Stefano Zacchini, Iacopo Ciabatti, Raffaele Guido Della Valle, Marcello Mazzani and Mauro Riccò

      Article first published online: 17 JUL 2014 | DOI: 10.1002/ejic.201402289

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      The synthesis and characterization of the new [Ni19Sb4(CO)26]4– cluster, as well as the synthesis, structure, magnetic characterization and electrical resistivity of the viologen salts of the previously known [Ni13Sb2(CO)24]n (n = 2, 3) anionic species are reported.

    7. Iron-Based Chromophores

      Heteroleptic Pyridyl-Carbene Iron Complexes with Tuneable Electronic Properties

      Thibaut Duchanois, Thibaud Etienne, Marc Beley, Xavier Assfeld, Eric A. Perpète, Antonio Monari and Philippe C. Gros

      Article first published online: 15 JUL 2014 | DOI: 10.1002/ejic.201402356

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      New iron-based chromophores with tuneable electronic properties have been prepared by mixing a pyridyl-terpyridine and a pyridyl-carbene ligand. The MLCT transition occurred at low energy upon protonation of pendant pyridine, with a wide absorption domain (450–650 nm), making the compounds promising for light-driven applications.

    8. Ethylene Oligomerisation

      Iminobisphosphines to (Non-)Symmetrical Diphosphinoamine Ligands: Metal-Induced Synthesis of Diphosphorus Nickel Complexes and Application in Ethylene Oligomerisation Reactions

      Pierre Boulens, Martin Lutz, Erwann Jeanneau, Hélène Olivier-Bourbigou, Joost N. H. Reek and Pierre-Alain R. Breuil

      Article first published online: 15 JUL 2014 | DOI: 10.1002/ejic.201402430

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      Alkyl-substituted symmetrical and nonsymmetrical diphosphinoamine nickel complexes have been prepared by using sulfonamido-based iminobisphosphines as ligand promoters. The complexes with basic substituents, activated by methylaluminoxane, oligomerise ethylene to short oligomers (C4–C8) with high activity. Fast codimerisation is observed, leading to highly branched C6 product distribution.

    9. Cu(I) and Fe(II)-Based Polymers

      A Heterometallo-Supramolecular Polymer with CuI and FeII Ions Introduced Alternately

      Md. Delwar Hossain, Jian Zhang, Rakesh K. Pandey, Takashi Sato and Masayoshi Higuchi

      Article first published online: 15 JUL 2014 | DOI: 10.1002/ejic.201402468

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      Utilizing different coordination structures of the metal ions, a new heterometallo-supramolecular polymer with alternately introduced CuI and FeII ions (polyCuFe) was synthesized by simple 0.5:0.5:1 complexation of CuI and FeII salts with an unsymmetrical ditopic ligand (L1) bearing phenanthroline and terpyridine moieties as the CuI and FeII coordination sites, respectively.

    10. Polyoxoaurates

      How Counterions Affect the Solution Structure of Polyoxoaurates: Insights from UV/Vis Spectral Simulations and Electrospray Mass Spectrometry

      Aleksandar Kondinski, Nina Vankova, Florian Schinle, Patrick Jäger, Oliver Hampe, Ulrich Kortz and Thomas Heine

      Article first published online: 15 JUL 2014 | DOI: 10.1002/ejic.201402494

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      The solution structure of the two known polyoxoaurates, [Au4As4O20]8– and [Au4Se4O16]4–, was elucidated by time-dependent DFT calculations, UV/Vis spectroscopy, and electrospray mass spectrometry. The combination of computational and experimental approaches allowed us to clarify the underlying structure–property relation and to explain the differences in the UV/Vis spectra of the two oxoaurates.

    11. Photophysics

      Elucidating the Origin of Enhanced Phosphorescence Emission in the Solid State (EPESS) in Cyclometallated Iridium Complexes

      Ashlee J. Howarth, Raissa Patia, David L. Davies, Francesco Lelj, Michael O. Wolf and Kuldip Singh

      Article first published online: 15 JUL 2014 | DOI: 10.1002/ejic.201402495

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      A new mechanism for enhanced phosphorescence emission in the solid state (EPESS) in cyclometallated Ir complexes with the general formula [Ir(CN)2(NO)] involving distortion of the six-membered chelate ring of the ancillary ligand is proposed.

  8. Short Communications

    1. Manganese Coordination Polymers

      Synthesis, Characterization, Magnetic and Catalytic Properties of a Ladder-Shaped MnII Coordination Polymer

      Smaragda Lymperopoulou, Maria Papastergiou, Maria Louloudi, Catherine P. Raptopoulou, Vassilis Psycharis, Constantinos J. Milios and John C. Plakatouras

      Article first published online: 15 JUL 2014 | DOI: 10.1002/ejic.201402419

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      A new ladder-shaped MnII coordination polymer (CP) with a N-substituted iminodiacetate ligand has been synthesized and characterized. It demonstrates catalytic activity as a heterogeneous catalyst for the epoxidation of alkenes in the presence of H2O2.

  9. Full Papers

    1. Luminescent Materials

      Aggregation-Induced Emission Activity in Iridium(III) Diimine Complexes: Investigations of Their Vapochromic Properties

      Parvej Alam, Maheswararao Karanam, Debashree Bandyopadhyay, Angshuman Roy Choudhury and Inamur Rahaman Laskar

      Article first published online: 15 JUL 2014 | DOI: 10.1002/ejic.201402222

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      Two new mono(diimine)-based complexes of iridium(III) have been synthesized. The two diimine complexes emit weak light in solution and strong light in the solid state, the strong light in the solid state arising from aggregation-induced emission activity. These complexes are useful as vapor-responsive luminescent materials and for sensing volatile organic compounds.

  10. Short Communications

    1. Gold Nanoparticles

      Seeding Growth Approach to Gold Nanoparticles with Diameters Ranging from 10 to 80 Nanometers in Organic Solvent

      Christoph Stanglmair, Sebastian P. Scheeler and Claudia Pacholski

      Article first published online: 11 JUL 2014 | DOI: 10.1002/ejic.201402467

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      A seeded-growth method has been developed to synthesize nearly monodisperse gold nanoparticles with diameters of up to 80 nm in toluene. Here, agglomeration of the gold nanoparticles in the course of the growth reaction did not negatively affect the size distribution and the morphology of the resulting nanoparticles.

  11. Full Papers

    1. Cluster Compounds

      Electronic Effect Related to the Nonuniform Distribution of Ionic Charges in Metal-Cluster Chalcogenide Halides

      Elena Levi, Doron Aurbach and Olivier Isnard

      Article first published online: 11 JUL 2014 | DOI: 10.1002/ejic.201402300

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      The bond valence model is valid for a wide family of cluster compounds with different nuclearities. On the basis of the separation of steric and electronic effects, the unusual distribution of anion valences around clusters is assigned to the nonuniform spreading of ionic charges in the crystal structure. Thus, stabilization in cluster compounds is explained by simple electrostatic interactions.

  12. Microreviews

    1. Stimuli-Responsive Materials

      Stimuli-Responsive Dynamic Gold Complexes

      Csaba Jobbágy and Andrea Deák

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

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

  13. Full Papers

    1. Heterometallic Complexes

      Heterobinuclear Zn–Ln and Ni–Ln Complexes with Schiff-Base and Carbacylamidophosphate Ligands: Synthesis, Crystal Structures, and Catalytic Activity

      Oleksiy V. Amirkhanov, Olesia V. Moroz, Kateryna O. Znovjyak, Tetiana Yu. Sliva, Larysa V. Penkova, Tetyana Yushchenko, Lukasz Szyrwiel, Irina S. Konovalova, Viktoriya V. Dyakonenko, Oleg V. Shishkin and Vladimir M. Amirkhanov

      Article first published online: 10 JUL 2014 | DOI: 10.1002/ejic.201402224

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      Synthesis and crystal studies of new binuclear 3d–4f complexes based on lanthanide motifs with carbacylamidophosphate ligands and moieties of ZnII and NiII with Schiff bases were carried out. The ability of the system to catalyze the intramolecular transesterification of 2-(hydroxypropyl)-p-nitrophenyl phosphate, which is extensively employed as an RNA model substrate, was tested.

    2. Photocatalysis

      Basic Molten Salt Route to Prepare Porous SrTiO3 Nanocrystals for Efficient Photocatalytic Hydrogen Production

      Hui Liu, Xianliu Chen, Shicheng Yan, Zhaosheng Li and Zhigang Zou

      Article first published online: 10 JUL 2014 | DOI: 10.1002/ejic.201402280

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      Porous SrTiO3 nanocrystals with large specific surface area and good crystallinity are synthesized by using a basic molten salt method. The nanocrystals exhibit efficient photocatalytic activity for hydrogen production owing to low carrier recombination and their increased number of reaction sites.

    3. Magnetic Properties

      Electric-Field Effects on Trimeric Mixed-Valence Clusters

      Sophia I. Klokishner, Marianna A. Roman and Oleg S. Reu

      Article first published online: 10 JUL 2014 | DOI: 10.1002/ejic.201402218

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      The manifestations of an external electric field on the magnetic and polarizability characteristics of trimeric mixed-valence clusters are investigated. The anisotropy of the cluster polarizability is predicted. External electric fields offer a unique possibility to manipulate the polarizability and magnetic characteristics of trimeric mixed-valence clusters.

    4. Spin Crossover

      Spin-State-Dependent Properties of an Iron(III) Hydrogenase Mimic

      Eileen Edler and Matthias Stein

      Article first published online: 9 JUL 2014 | DOI: 10.1002/ejic.201402295

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      A pentacoordinate FeIII complex shows spin-state-dependent features, for example, its structural parameters and the torsional profile of the axial ligand. The intermediate state is confirmed to be the ground state, but the ordering of spin states is dependent on the c3 parameter in hybrid DFT functionals. Thermodynamic analysis suggests that this compound is a possible spin-crossover complex.

  14. Short Communications

    1. Electron-Transfer Reactions

      Electron-Transfer Rate Enhancements in Nanosized Waterpools

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

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

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

    2. Borate–Phosphates

      The Effect of the Ratio of [M/(B+P)] on the Configuration of Anionic Groups: ­Synthesis of the Borate–Phosphate LiPb4(BO3)(PO4)2

      Shengshi Huang, Hongwei Yu, Jian Han, Shilie Pan, Qun Jing, Ying Wang, Lingyun Dong, Hongping Wu, Zhihua Yang and Xian Wang

      Article first published online: 9 JUL 2014 | DOI: 10.1002/ejic.201402389

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      Statistical analysis and experiments results show that regulating the [M/(B+P)] ratio is an effective strategy to synthesize borate–phosphates. Guided by this idea, the first example in the Li2O–PbO–B2O3–P2O5 system, LiPb4(BO3)(PO4)2, is synthesized. More interesting, it possesses a 3D structure with a corrugated 2D layer of [B2Pb8O18] that is further connected by a [LiP2O8] chain.

  15. Full Papers

    1. Luminescence

      Ca3Si2O4N2:Ce3+,Li+ Phosphor for the Generation of White-Light-Emitting Diodes with Excellent Color Rendering Index Values

      Chien-Hao Huang, Yi-Chen Chiu and Wei-Ren Liu

      Article first published online: 8 JUL 2014 | DOI: 10.1002/ejic.201402052

      Thumbnail image of graphical abstract

      A blue-emitting Ca3Si2O4N2:Ce3+,Li+ phosphor is synthesized by a solid-state reaction. The crystal structure, luminescence properties, diffuse reflection spectrum, and thermal quenching of the phosphor are investigated. The phosphor is also a promising blue-emitting phosphor for application in white-light-emitting diode (LED) package lamps with excellent color rendering index (CRI) values.

  16. Short Communications

    1. Metalloligands

      Close Correlation between Metal Oxidation States and Molecular Structures in a Cobalt–Gold Multinuclear Coordination System with Mixed D-Penicillaminate and Tripodal Triphosphine

      Yuji Hashimoto, Nobuto Yoshinari, Natsuko Matsushita and Takumi Konno

      Article first published online: 7 JUL 2014 | DOI: 10.1002/ejic.201402531

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      [Au3(tdme)(D-pen)3]3–, which possesses D-penicillaminate (D-pen) arms connected by a 1,1,1-tris[(diphenylphosphino)methyl]ethane (tdme) backbone, is designed and synthesized. This metalloligand adopts two coordination modes (bridging/chelating) coupled with two oxidation states of the binding cobalt ions (+II/+III), which leads to the formation of air-stable CoII3AuI6 and CoIIIAuI3.

  17. Full Papers

    1. Hydrolysis

      Use of Organomolybdenum Compounds for Promoted Hydrolysis of Phosphoester Bonds in Aqueous Media

      Ana C. Gomes, Carla A. Gamelas, José A. Fernandes, Filipe A. Almeida Paz, Patrique Nunes, Martyn Pillinger, Isabel S. Gonçalves, Carlos C. Romão and Marta Abrantes

      Article first published online: 7 JUL 2014 | DOI: 10.1002/ejic.201402071

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      The dissolution of [{(η5-Ind)Mo(CO)2(μ-Cl)}2] (Ind = indenyl) in N,N-dimethylformamide (DMF) results in the formation of [(η3-Ind)Mo(CO)2Cl(DMF)2], the aerial oxidation of which leads to [Mo2O2(DMF)4(μ-O)2Cl2]. [{(η5-Ind)Mo(CO)2(μ-Cl)}2] and [Mo2O2(DMF)4(μ-O)2Cl2] are examined as promoters of phosphoester bond hydrolysis of para-nitrophenylphosphate (pNPP) in aqueous solution at 55 °C.

    2. Synthetic Nitrogen Fixation

      (Dinitrogen)molybdenum Complexes Supported by Asymmetric Silicon-Centered Tripod Ligands: Steric and Electronic Influences on the Coordination of Mono- and Diphosphine Coligands

      Henning Broda, Jan Krahmer and Felix Tuczek

      Article first published online: 4 JUL 2014 | DOI: 10.1002/ejic.201402273

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      A synthetic route to silicon-centered mixed dialkylphosphine/diarylphosphine tripod ligands has been established leading to nine new Mo–N2 complexes. The resulting structures and the activation of the coordinated N2 ligands are discussed with respect to steric and electronic effects.

  18. Short Communications

    1. Strain Effects

      Uniaxial Strain Effect of the Moderately Dimerized Molecular Conductor β-(meso-DMBEDT-TTF)2PF6

      Yohei Nishida, Takayuki Isono, Akira Ueda and Hatsumi Mori

      Article first published online: 4 JUL 2014 | DOI: 10.1002/ejic.201402463

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      Band calculations and resistivity measurements under uniaxial strain are performed for the moderately dimerized molecular conductor β-(meso-DMBEDT-TTF)2PF6 [DMBEDT-TTF = dimethylbis(ethylenedithio)tetrathiafulvalene]. Under uniaxial strain along the c and (ab) axes, intersite electronic correlations contribute and superconducting (SC) behavior is observed, which indicates that the SC state is deeply related to the charge-ordered state.

  19. Full Papers

    1. Redox Chemistry

      Experimental and DFT/Time-Dependent DFT Studies on Neutral and One-Electron-Reduced Quinoxaline and Pyrazine Precursors and Their Mononuclear (PdII, PtII) Derivatives

      Maria Pia Donzello, Giorgia De Mori, Elisa Viola, David Futur, Zhen Fu, Corrado Rizzoli, Luisa Mannina, Enrico Bodo, Maria Luisa Astolfi, Claudio Ercolani and Karl M. Kadish

      Article first published online: 4 JUL 2014 | DOI: 10.1002/ejic.201402282

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      6,7-Dicyano-2,3-di(2-pyridyl)quinoxaline, [(CN)2Py2Qx], its mononuclear complex [(CN)2Py2QxPtCl2] and the 2,3-dicyanopyrazine compounds [(CN)2Py2Pyz] and its PtII complex [(CN)2Py2PyzPtCl2], carrying 2-pyridyl rings were studied as neutral and mononegatively charged species by electrochemical and UV/Vis spectral measurements. The obtained data were interpreted by DFT/time-dependent DFT studies.

  20. Short Communications

    1. Isomerization

      Reductive Behavior of [Fe2(CO)42-dmpe){μ-(SCH2)2NBn}]: Effect of Symmetrization on the Rotated Conformation in FeI-FeI Models of [2Fe]H Subsite of [Fe-Fe]­H2ases

      Luca De Gioia, Catherine Elleouet, Sabrina Munery, François Y. Pétillon, Philippe Schollhammer, Jean Talarmin and Giuseppe Zampella

      Article first published online: 4 JUL 2014 | DOI: 10.1002/ejic.201402335

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      Electrosynthesis, through an electron-transfer-catalyzed process, and structural characterization of the symmetrical complex [Fe2(CO)4(μ-dmpe){μ-(SCH2)2NBn}] [dmpe = 1,2-bis(dimethylphosphino)ethane] afford straight experimental evidence that desymmetrization is required to promote an inverted pyramidal conformation in this class of model compounds of the [2Fe]H subsite of [Fe-Fe]H2ases.

    2. Click Chemistry

      A Luminescent Ruthenium Azide Complex as a Substrate for Copper-Catalyzed Click Reactions

      Anne Kroll, Katharina Monczak, Dieter Sorsche and Sven Rau

      Article first published online: 3 JUL 2014 | DOI: 10.1002/ejic.201402395

      Thumbnail image of graphical abstract

      A new azide-functionalized 2,2′-bipyridine and its polypyridyl–ruthenium(II) complex are both suitable for click reactions. The substitution has a minor effect on the photophysical properties of the complex. Hence, the presented azide complex is a promising building block for the straightforward synthesis of a variety of photoactive click derivatives.

  21. Full Papers

    1. Tetrametallaborane Clusters

      The Buildup of Eight-Vertex Tetrametallaborane Clusters: Bisdisphenoidal versus Tetracapped Tetrahedral Structures

      Alexandru Lupan and R. Bruce King

      Article first published online: 2 JUL 2014 | DOI: 10.1002/ejic.201402363

      Thumbnail image of graphical abstract

      Density functional theory predicts the experimentally known bisdisphenoidal structure for Cp4M4B4H4 (M = Co, Ni) but a tetracapped tetrahedral structure for Cp4Fe4B4H4. Addition of BH units to Cp4M4 or Cp4M4B2H2 to give Cp4M4B4H4 is predicted to be highly exothermic for all three metals.

    2. Photoelectrochemical Cells

      Synthesis and Photoelectrochemical Properties of Efficient Photoanodes Built from Fe2O3/NiO Heterostructures

      Weiqiang Fan, Chao Zhang, Hongye Bai, Xiaoqiang Yu and Weidong Shi

      Article first published online: 2 JUL 2014 | DOI: 10.1002/ejic.201402416

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      New Fe2O3/NiO heterostructures have been successfully synthesized. Variation of the quantity of NiO can significantly affect their microstructures and photoelectrochemical properties.

    3. Carbon Nitride Nanorods

      Graphitic Carbon Nitride Nanorods for Photoelectrochemical Sensing of Trace Copper(II) Ions

      Li Xu, Jiexiang Xia, Leigang Wang, Haiyan Ji, Jing Qian, Hui Xu, Kun Wang and Huaming Li

      Article first published online: 2 JUL 2014 | DOI: 10.1002/ejic.201402051

      Thumbnail image of graphical abstract

      A metal-free polymeric material, graphitic carbon nitride (g-C3N4) nanorods, has been designed and fabricated by means of hydrothermally treated bulk g-C3N4 using NH4Cl. A highly selective and sensitive photoelectrochemical (PEC) sensing platform based on the g-C3N4 nanorods has also been developed for detecting the trace copper(II) ions in aqueous solution.

    4. Heterometallic Complexes

      Trinuclear Early/Late-Transition-Metal Thiolate Complexes

      Andreas Eichhöfer, Vasyl Andrushko, Tilmann Bodenstein and Karin Fink

      Article first published online: 1 JUL 2014 | DOI: 10.1002/ejic.201402069

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      The paper presents the synthesis, structural characterisation, magnetic and optical properties, along with an analysis by quantum chemical calculations of a heterometallic vanadium(II)/cobalt(II) as well as a vanadium(II)/nickel(II) thiolato complex.

    5. Actinide Complexation

      The Role of Residual Charges in the Interaction between NpO2+ and Th4+ Cations: Spectrophotometric and Computational Studies

      Parveen Kumar Verma, Priyanath Pathak, Arunasis Bhattacharyya, Dattaprasad Ravaji Prabhu, Tapan Kumar Ghanty and Prasanta Kumar Mohapatra

      Article first published online: 30 JUN 2014 | DOI: 10.1002/ejic.201402211

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      Spectrophotometric studies have been carried out in order to understand the thermodynamics of the interaction of the NpO2+ cation with Th4+ at varying nitric acid and thorium concentrations. This interaction appears to be both exothermic and endothermic depending on the nitric acid concentration. DFT calculations suggest that the NpO2+–Th4+ interaction is stronger than that of the NpO2+–UO22+ pair.

    6. 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.

    7. Dinitrosyliron Complexes

      New Members of a Class of Monomeric {Fe(NO)2}10 Dinitrosyliron Complexes and a Dimeric {Fe(NO)2}10–{Fe(NO)2}10 Dinitrosyliron Complex

      Feng-Chun Lo, Yi-Chieh Ho, Po-Ya Chang, Gene-Hsiang Lee, Ting-Shen Kuo, Jeng-Lung Chen and Chien-Hong Chen

      Article first published online: 27 JUN 2014 | DOI: 10.1002/ejic.201402370

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      The countercation functions to modulate the formation of monomeric {Fe(NO)2}10 dinitrosyliron complex (DNIC) 4 or dimeric {Fe(NO)2}10–{Fe(NO)2}10 DNIC 5, which is demonstrated upon reduction of {Fe(NO)2}9 DNICs [cation][(NO)2Fe(SC6H4-o-NH2)2] (6) {cation = K-18-crown-6-ether (6a), [PPh4] (6b)}.

    8. Mixed-Valent Compounds

      Coexistence of Localized and Itinerant Electrons in the Double-Perovskite Ba2Fe2/3Mo4/3O6

      Carlos A. López, Martín E. Saleta, José C. Pedregosa, Rodolfo D. Sánchez, José A. Alonso and María T. Fernández-Díaz

      Article first published online: 27 JUN 2014 | DOI: 10.1002/ejic.201402241

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      A double-perovskite Ba2Fe2/3Mo4/3O6 with Fe/Mo (1:2 ratio) mixed valence states was obtained. From a synthesis under reducing conditions we have stabilized the coexistence of itinerant (associated with Mo) and localized (associated with Fe) electrons. This coexistence of electrons leads to non-negligible magnetoresistance properties.

    9. Digallium Compounds

      Treatment of the Digallium Compound R2Ga–GaR2 [R = CH(SiMe3)2] with Functionalized Dicarboxylic Acids: Macrocycles, Hydrogen Bonding, and Sulfur–Sulfur Closed-Shell Interactions

      Werner Uhl, Christina Stefaniak, Alexander Hepp and Jutta Kösters

      Article first published online: 26 JUN 2014 | DOI: 10.1002/ejic.201402172

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      Ga–Ga bonds act as effective templates for the generation of macrocyclic compounds with dicarboxylato spacer ligands in the bridging positions. Hydrogen bonds or sulfur–sulfur closed-shell interactions were observed with functionalized amino or dithio spacer ligands.

    10. Pincer Ligand Complexes

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

      Yoshihiro Miyake, Kazunari Nakajima, Yu Higuchi and Yoshiaki Nishibayashi

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

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

    11. Palladium Complexes

      Alternative Synthetic Methods for PEPPSI-Type Palladium Complexes

      Kerry-Ann Green, Paul T. Maragh, Kamaluddin Abdur-Rashid, Alan J. Lough and Tara P. Dasgupta

      Article first published online: 25 JUN 2014 | DOI: 10.1002/ejic.201402317

      Thumbnail image of graphical abstract

      Several PEPPSI-type complexes (PEPPSI = pyridine-enhanced precatalyst preparation stabilization and initiation) were successfully prepared in good yields by a new synthetic method involving hydrohalides of pyridine, azolium salts and palladium bisacetylacetonate.

    12. Coordination Polymers

      Structures and Magnetic Properties of Manganese(II) Compounds Based on Chains with Simultaneous Carboxylate and Pseudohalide Bridges

      Guang-Mei Zhuang, Xiu-Bing Li, Yan-Qing Wen, Chun-Yan Tian and En-Qing Gao

      Article first published online: 25 JUN 2014 | DOI: 10.1002/ejic.201402287

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      Various zwitterionic carboxylate ligands lead to 1D, 2D and 3D MnII coordination polymers based on distinct chains with mixed carboxylate and pseudo-halide (azide or cyanate) bridges. Magneto-structural correlations are discussed.

    13. DNA Cleavage

      Phosphate Diester Cleavage, DNA Interaction and Cytotoxic Activity of a Bimetallic Bis(1,4,7-triazacyclononane) Zinc Complex

      Diego Montagner, Valentina Gandin, Cristina Marzano and Andrea Erxleben

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402319

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      A new bimetallic Zn complex with a phenolate scaffold ligand with two aza-crown binding sites has been synthesized and characterized. DNA binding, cleavage and cytotoxicity results are reported.

    14. Molecular Magnetism

      Tetranuclear [Mn2Co2], [Mn2Fe2], and [Mn2Mn2] Complexes with Defective Double-Cubane Cores and Phenoxo and Oxo Bridges: Syntheses, Crystal Structures, and Electronic Properties

      Pijush Malpaharia, Koushik Pramanik, Jean-Pierre Costes, Jean-Pierre Tuchagues, Brian Moulton, Michael J. Zaworotko, Babulal Das and Swapan K. Chandra

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402191

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      The syntheses, crystal structures, and electronic properties of three tetranuclear [Mn2Co2], [Mn2Fe2], and [Mn2Mn2] compounds are described. These complexes possess defective double-cubane [Mn2M2O2]8+ cores and are interesting examples that show how small structural changes in molecule-based magnetic compounds can strongly affect the overall electronic properties.

    15. Macroions

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

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

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

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

    16. Tellurenyl Chloride Adducts

      A Facile Route for Stabilizing Highly Reactive ArTeCl Species Through the Formation of T-Shaped Tellurenyl Chloride Adducts: quasi-Planar Zwitterionic [HPy*]TeCl2 and [HPm*]TeCl2; Py* = 2-pyridyl, Pm* = 2-(4,6-dimethyl)pyrimidyl

      Victor N. Khrustalev, Zhanna V. Matsulevich, Julia M. Lukiyanova, Rinat R. Aysin, Alexander S. Peregudov, Larissa A. Leites and Alexander V. Borisov

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402294

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      Two new stable T-shaped tellurenyl chloride adducts, [HPy*]TeCl2 (1) and [HPm*]TeCl2 (2) [Py* = 2-pyridyl, Pm* = 2-(4,6-dimethyl)pyrimidyl], act as close analogs of highly unstable monomeric Py*TeCl and Pm*TeCl. The quasi-planar zwitterionic structures of 1 and 2 were studied by experimental and theoretical methods. Thus, a novel facile route to stabilize highly reactive Ar*TeCl species (Ar* = N-functionalized aryl) by addition of an HCl molecule has been demonstrated.

    17. Nickel Hydride Electrocatalysts

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

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

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

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

    18. Conducting Materials

      Tuning the Electronic Properties of Piezoresistive Bilayer Films Based on α-(BEDT-TTF)2I3

      Victor Lebedev, Elena Laukhina, Vladimir Laukhin, Concepció Rovira and Jaume Veciana

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402276

      Thumbnail image of graphical abstract

      The electrical properties of the conducting layer of piezoresistive all-organic flexible bilayer films are fine tuned without changing their high strain sensitivity.

  22. Microreviews

    1. Dinuclear Technetium Complexes

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

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

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

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

  23. Full Papers

    1. Antitumor Agents

      Substitution-Modulated Anticancer Activity of Half-Sandwich Ruthenium(II) Complexes with Heterocyclic Ancillary Ligands

      Raja Mitra and Ashoka G. Samuelson

      Article first published online: 24 JUN 2014 | DOI: 10.1002/ejic.201402205

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      The substituents of aromatic heterocyclic ancillary ligands controls the anticancer activity of bioorganometallic half-sandwich ruthenium complexes. The chloro- and bromo-substituted complexes are less potent than the fluoro-substituted complexes.

    2. Nanoparticles

      Impact of the Presence of Octadecylamine on the Properties of Hydrothermally Prepared CoFe2O4 Nanoparticles

      Violetta Georgiadou and Catherine Dendrinou-Samara

      Article first published online: 18 JUN 2014 | DOI: 10.1002/ejic.201402323

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      Octadecylamine is used in the hydrothermal synthesis of CoFe2O4 nanoparticles (NPs) and serves as the foundation of the NP surface functionalization. Three different paths for surface chemistry for relaxometric measurements were performed, and the relaxivity of the magnetic fluorescent CoFe2O4 NPs is promising.

    3. Cycloruthenated Complexes

      Cycloruthenation of N-(Naphthyl)salicyl­aldimine and Related Ligands: Utilization of the Ru–C Bond in Catalytic Transfer Hydrogenation

      Jayita Dutta, Michael G. Richmond and Samaresh Bhattacharya

      Article first published online: 17 JUN 2014 | DOI: 10.1002/ejic.201402236

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      N-(Naphthyl)-4-R-salicylaldimines (R = OCH3, H, Cl; H2L1–H2L3) and 2-hydroxy-N-(naphthyl)naphthaldimine (H2L4) react with [Ru(PPh3)2(CO)2Cl2], undergoing C–H bond activation at the peri position, to afford complexes of the type [Ru(PPh3)2(L)(CO)] (L = L1L4), which can efficiently catalyze the transfer hydrogenation of carbonyl compounds.

    4. Charge-Transfer Salts

      An Organic Metal Derived from a Selenium Analogue of Benzothienobenzothio­phene

      Toshiki Higashino, Tomofumi Kadoya, Shohei Kumeta, Kohei Kurata, Tadashi Kawamoto and Takehiko Mori

      Article first published online: 16 JUN 2014 | DOI: 10.1002/ejic.201402221

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      A charge-transfer salt of the organic semiconductor benzoselenobenzoselenophene (BSBS) with TaF6 is prepared. (BSBS)2TaF6 has a strong one-dimensional character with tetragonal crystal symmetry. In comparison with the sulfur analogue, the resistance jump temperature is reduced, and the low-temperature resistance increase is diminished.

    5. Radical Complexes

      Detailed Geometric and Electronic Structures of a One-Electron-Oxidized Ni Salo­phen Complex and Its Amido Derivatives

      Laureline Lecarme, Linus Chiang, Christian Philouze, Olivier Jarjayes, Tim Storr and Fabrice Thomas

      Article first published online: 5 JUN 2014 | DOI: 10.1002/ejic.201402265

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      The radical complexes depicted feature a near-IR (NIR) transition. Time-dependent DFT (TD-DFT) calculations reveal that its origin differs and strongly depends on the linker between the central ring and the phenol rings. Depending on the linker, it is an intervalence charge transfer (IVCT) transition, an intraligand charge transfer (LLCT), or acquires ligand-to-metal charge transfer (LMCT) character.

    6. Supramolecular Conductors

      Effects of Solvent Additives on the Crystal Architecture of Supramolecular Conductors Based on Diiodo(ethylenedithio)tetraselenafulvalene and Indium Tetrahalide Anions

      Tatsuro Imakubo and Mitsuaki Kobayashi

      Article first published online: 5 JUN 2014 | DOI: 10.1002/ejic.201400127

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      The utilization of solvent additives made it possible to modify the crystal quality, structure, morphology, and composition of cation radical salts based on the π donor diiodo(ethylenedithio)tetraselenafulvalene and indium tetrahalide anions. The addition of a few drops of water as the solvent additive induced the in situ formation of the [InCl4(H2O)2] anion.

    7. 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

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      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.

    8. Photoconductors

      Giant Photoconductivity in NMQ[Ni(dmit)2]

      Toshio Naito, Tomoaki Karasudani, Naoki Nagayama, Keishi Ohara, Kensuke Konishi, Shigeki Mori, Takahiro Takano, Yukihiro Takahashi, Tamotsu Inabe, Shota Kinose, Sadafumi Nishihara and Katsuya Inoue

      Article first published online: 27 MAY 2014 | DOI: 10.1002/ejic.201402035

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      NMQ[Ni(dmit)2] (NMQ = N-methylquinolinium, dmit = 1,3-dithiol-2-thione-4,5-dithiolate exhibits an unusually high ratio of photoconductivity to dark conductivity exclusively under irradiation (375 nm).

    9. POM-Tethered Diblock Copolymers

      Supramolecular Assemblies of Polyoxometalate-Tethered Diblock Copolymers with Tunable Sizes in N-Methyl-2-pyrrolidone/Toluene Mixed Solvents

      Fadi Haso, Ruixin Wang, Panchao Yin, Jing Zhou, Lu Jin, Zhonghua Peng and Tianbo Liu

      Article first published online: 27 MAY 2014 | DOI: 10.1002/ejic.201402201

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      Rod–coil diblock copolymers, consisting of poly(3-hexylthiophene-2,5-diyl) as the rod block and a POM tethered to a polystyrene derivative as the coil block, self-assemble into vesicles in polar solvents. The vesicle size can be controlled by changing the solvent polarity. A transition to reverse vesicles with controllable size is achieved when the solvent is relatively nonpolar.

    10. Dithiolene Complexes

      5-Methylthiophene-2,3-dithiolene Transition Metal Complexes

      Ana I. S. Neves, Isabel C. Santos, Joana T. Coutinho, Laura C. J. Pereira, Rui T. Henriques, Elsa B. Lopes, H. Alves, Manuel Almeida and Dulce Belo

      Article first published online: 22 MAY 2014 | DOI: 10.1002/ejic.201402048

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      A family of transition metal complexes [M(α-mtpdt)2] (M = Au, Ni, Fe, Cu, Co, Pt and Pd) with a methyl-substituted thiophenedithiolene ligand (α-mtpdt) are synthesised. The Ni and Au complexes can be obtained in their neutral state as stable compounds; they are fairly soluble in organic solvents and have semiconducting properties.

    11. Semiconductor Crystal Engineering

      Synthesis, Crystal Structure, and Characterization of the Charge-Transfer Salt (BEDT-TTF)[Fe(C2O4)Cl2](CH2Cl2), {BEDT-TTF = Bis(ethylenedithio)tetrathiafulvalene}

      Bin Zhang, Yan Zhang, Zengqiang Gao, Guangcai Chang, Shaokui Su, Dongwei Wang, Yanjun Guo and Daoben Zhu

      Article first published online: 20 MAY 2014 | DOI: 10.1002/ejic.201402112

      Thumbnail image of graphical abstract

      The title compound has been synthesized and studied, and it was found that the donor layers in the organic–inorganic hybrid charge-transfer salt, which is composed of BEDT-TTF1.0+ dimers and CH2Cl2, are separated by zigzaged anion chains. The compound is a semiconductor and shows strong antiferromagnetic interactions between the oxalate-bridged metal atoms.

    12. Mixed-Valence Compounds

      Synthesis and Properties of a Mixed-Valence Compound with Single-Step Tunneling and Multiple-Step Hopping Behavior

      Rim Makhoul, Yuki Kumamoto, Akira Miyazaki, Frédéric Justaud, Frédéric Gendron, Jean-François Halet, Jean-René Hamon and Claude Lapinte

      Article first published online: 19 MAY 2014 | DOI: 10.1002/ejic.201402022

      Thumbnail image of graphical abstract

      The complex trans-[Cp*(dppe)Fe–C≡C–TTFMe2–C≡C–Fe(dppe)Cp*][PF6] [Cp* = η5-C5Me5, dppe = 1,2-bis(diphenylphosphanyl)ethane, TTF = tetrathiafulvalene] is a class II mixed-valence compound in which the spin density varies with the respective orientation of the metal termini. Intramolecular electron transfer occurs through single-step tunneling and multiple-step hopping mechanisms.

  24. Short Communications

    1. Isotope Effect of Thermopower

      Isotope Effect of Thermopower in the TTFCOONH3Ph Single Crystal

      Yuka Kobayashi, Satoshi Sumi, Takeshi Terauchi, Hideo Iwai, Akihiro Tanaka, Yoshitaka Matsushita and Akira Sato

      Article first published online: 16 MAY 2014 | DOI: 10.1002/ejic.201402055

      Thumbnail image of graphical abstract

      A large isotope effect of thermopower has been found for semiconducting TTFCOONH3Ph and its deuteriated form, TTFCOOND3Ph. The origin of the isotope effect has been investigated based on chemical and physical characterizations using high-quality single crystals.

  25. Full Papers

    1. Molecular Superconductors

      Four Molecular Superconductors Isolated as Nanoparticles

      Dominique de Caro, Christophe Faulmann, Lydie Valade, Kane Jacob, Imane Chtioui, Soukaina Foulal, Pascale de Caro, Manon Bergez-Lacoste, Jordi Fraxedas, Belén Ballesteros, James S. Brooks, Eden Steven and Laurel E. Winter

      Article first published online: 16 MAY 2014 | DOI: 10.1002/ejic.201402007

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      Four molecular superconductors have been prepared as nanoparticles by using mainly electrochemical synthesis. Among them, (TMTSF)2ClO4 (TMTSF = tetramethyltetraselenafulvalene) has been the most studied up to now and, like the bulk single crystals, it exhibits superconductivity.

    2. Single-Molecule Magnets

      Slow Magnetic Relaxation in a Redox-Active Tetrathiafulvalene-Based Ferromagnetic Dysprosium Complex

      Fabrice Pointillart, Stéphane Golhen, Olivier Cador and Lahcène Ouahab

      Article first published online: 14 MAY 2014 | DOI: 10.1002/ejic.201402181

      Thumbnail image of graphical abstract

      The dinuclear coordination complex [Dy(tta)2(L1)(L2)]2·2(CH2Cl2) [tta = 2-thenoyltrifluoroacetonate, L1 and L2 = tetrathiafulvalene (TTF) ligands] shows significant ferromagnetic interactions between both DyIII ions. Owing to the two different TTF ligands, the molecule is a multiredox system. It also displays single-molecule magnetic behaviour with the Ising ground state MJ = ±15/2.

  26. Short Communications

    1. Organometallic Gold Compounds

      New Gold(I) Organometallic Compounds with Biological Activity in Cancer Cells

      Benoît Bertrand, Andreia de Almeida, Evelien P. M. van der Burgt, Michel Picquet, Anna Citta, Alessandra Folda, Maria Pia Rigobello, Pierre Le Gendre, Ewen Bodio and Angela Casini

      Article first published online: 13 MAY 2014 | DOI: 10.1002/ejic.201402248

      Thumbnail image of graphical abstract

      Organometallic N-heterocyclic carbene gold(I) complexes bearing a fluorescent coumarin ligand are synthesized, and their antiproliferative effects in normal and tumor cells in vitro are studied. Their biological properties may be due to inhibition of thioredoxin reductases. Fluorescence confocal microscopy allows the uptake of the compounds in cancer cells to be observed.

  27. Full Papers

    1. Coordination Chemistry

      Cyanido-Bearing Cobalt(II/III) Metalloligands – Synthesis, Crystal Structure, and Magnetic Properties

      Maria-Gabriela Alexandru, Diana Visinescu, Nadia Marino, Giovanni De Munno, Julia Vallejo, Francesc Lloret and Miguel Julve

      Article first published online: 9 MAY 2014 | DOI: 10.1002/ejic.201402190

      Thumbnail image of graphical abstract

      Three diamagnetic CoIII complexes PPh4[Co(L)(CN)4] [L = ethylenediamine (en), 1; 2-(aminomethyl)pyridine (ampy), 2; 1,10-phenanthroline (phen), 3] and one CoII complex PPh4[Co(dmphen)(CN)3] (4, dmphen = 2,9-dimethyl-1,10-phenanthroline) were obtained and characterized by single-crystal XRD and FTIR spectroscopy. Complex 4 forms weakly antiferromagnetically coupled CoII···CoII supramolecular dimers.

    2. Self-Assembly

      Exploring the Building-Block Potential of Readily Accessible Chiral [Zn(salen)] Complexes

      Eddy Martin, Marta Martínez Belmonte, Eduardo C. Escudero-Adán and Arjan W. Kleij

      Article first published online: 8 MAY 2014 | DOI: 10.1002/ejic.201402101

      Thumbnail image of graphical abstract

      A convenient method for the synthesis of a series of chiral [Zn(salen)] [salen = N,N′-bis(salicylidene)ethylenediamine dianion] complexes based on a 1,2-diphenylethanediamine backbone has been developed. These complexes have been used to assemble multinuclear supramolecular assemblies of which the solid-state and solution properties were determined. These chiral [Zn(salen)] complexes hold promise as molecular building blocks with modular characteristics.

    3. Iron Phthalocyanines

      Layered Salts with Iron Hexadeca­chlorophthalocyanine Anions – The Formation of [{FeCl16Pc}2]3– Dimers Containing [FeICl16Pc(2–)] and Diamagnetic [Fe0Cl16Pc(2–)]2–

      Dmitri V. Konarev, Alexey V. Kuzmin, Manabu Ishikawa, Yoshiaki Nakano, Maxim A. Faraonov, Salavat S. Khasanov, Akihiro Otsuka, Hideki Yamochi, Gunzi Saito and Rimma N. Lyubovskaya

      Article first published online: 7 MAY 2014 | DOI: 10.1002/ejic.201400126

      Thumbnail image of graphical abstract

      Two salts with iron hexadecachlorophthalocyanine anions were obtained. (PPN+)[(FeICl16Pc)]·Solvent (1) has a layered structure with π–π stacking columns. (TBA+)3[(FeCl16Pc)23–] (2) contains (FeCl16Pc)23– dimers with a {FeICl16Pc(2–)} monoanion and a {Fe0Cl16Pc(2–)}2– dianion connected through a Fe–Fe bond. There is no noticeable charge transfer from the iron atoms to the phthalocyanine macrocycles in 2.

  28. 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

      Thumbnail image of graphical abstract

      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.

  29. 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

      Thumbnail image of graphical abstract

      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.

  30. 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

      Thumbnail image of graphical abstract

      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.

  31. 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

      Thumbnail image of graphical abstract

      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

      Thumbnail image of graphical abstract

      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

      Thumbnail image of graphical abstract

      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

      Thumbnail image of graphical abstract

      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

      Thumbnail image of graphical abstract

      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

      Thumbnail image of graphical abstract

      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

      Thumbnail image of graphical abstract

      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.

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