European Journal of Inorganic Chemistry

Cover image for Vol. 2014 Issue 25

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

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.965

ISI Journal Citation Reports © Ranking: 2013: 10/44 (Chemistry Inorganic & Nuclear)

Online ISSN: 1099-0682

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

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  1. 1 - 89
  1. Full Papers

    1. Energetic Ionic Salts

      Synthesis and Characterization of the Nitrophenol Energetic Ionic Salts of 5,6,7,8-Tetrahydrotetrazolo[1,5-b][1,2,4]triazine

      Jin-Ting Wu, Jian-Guo Zhang, Xin Yin, Piao He and Tong-Lai Zhang

      Article first published online: 1 SEP 2014 | DOI: 10.1002/ejic.201402337

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      Three nitrogen-rich energetic salts of 5,6,7,8-tetrahydrotetrazolo[1,5-b][1,2,4]triazine (TZTN) have been prepared and characterized by single-crystal X-ray diffraction analysis. The salts exhibit excellent detonation performance and combine good thermal stabilities with acceptable sensitivities.

    2. Schiff-Base Complexes

      Main-Chain Oligomers from NiII- and CuII-Centered Unsymmetrical N2O2 Schiff-Base Complexes: Synthesis and Spectral, Structural, and Second-Order Nonlinear Optical Properties

      Salvador Celedón, Vincent Dorcet, Thierry Roisnel, Anu Singh, Isabelle Ledoux-Rak, Jean-René Hamon, David Carrillo and Carolina Manzur

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402469

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      The esterification of binuclear phenol and carboxylic acid functionalized ferrocenyl-containing metal-centered Schiff-base complexes (M = Ni, Cu) in the presence of N,N′-dicyclohexylcarbodiimide and dmap afforded their corresponding main-chain oligomers. They are formed of approximately six monomeric units, are redox active, and exhibit good thermal stability and high second-order NLO responses.

    3. Trimetallic Ag Complexes

      Triangular [Ag3]3+ Complexes Supported by Picolyl-Substituted N-Heterocyclic Carbene Ligands

      Lyndsay B. Munro and Vincent J. Catalano

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402483

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      A series of 12 picolyl-substituted benzimidazolylidene- and imidazolinylidene-based N-heterocyclic carbene ligands have been prepared. Eleven underwent complexation with AgI to form trimetallic complexes with short AgI–AgI metal–metal separations. In solution, all but one of these complexes are dynamic and dissociate and exchange ligands.

    4. Mechanism of Palladium Catalysis

      Mechanistic Insights into the PdII-Catalyzed Chemoselective N-Demethylation vs. Cyclometalation Reactivity Pathways in 1-Aryl-N,N-dimethylethanamines

      Jeanette See Leng Yap, Yi Ding, Xiang-Yuan Yang, Jonathan Wong, Yongxin Li, Sumod A. Pullarkat and Pak-Hing Leung

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402547

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      Two structurally isomeric substituted N,N-dimethylethanamines have been prepared. Treatment of one isomer with PdII ions generated the ortho-metalated complex, whilst the other isomer resulted in the unexpected chemoselective C–N bond cleavage to afford the corresponding secondary amine.

    5. Ambiphilic Ligands

      Synthesis, Structures and Coordination Chemistry of Singly Bridged Phosphane-Boranes with Coordinately Unsaturated Platinum Group Metals

      Victoria K. Greenacre, Melvyn B. Ansell, S. Mark Roe and Ian R. Crossley

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402649

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      The synthesis and characterisation of a range of singly bridged phosphane-boranes is described. Their coordination complexes with co-ordinately unsaturated platinum group metals demonstrate a propensity for adopting structures with pendant borane moieties occupying distal positions.

    6. Spin-Crossover Complexes

      Unusual Solvent Dependence of a Molecule-Based FeII Macrocyclic Spin-Crossover Complex

      Hongfeng Wang, Chiara Sinito, Abdellah Kaiba, José Sanchez Costa, Cédric Desplanches, Philippe Dagault, Philippe Guionneau, Jean-François Létard, Philippe Negrier and Denise Mondieig

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402666

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      The solvent dependence of spin-crossover behavior and metastability of the FeII complex [FeL222N3O2(CN)2]·H2O were investigated. Compared with the pristine and the dehydrated complex, the rehydrated complex shows enhanced metastability and an increased spin-transition temperature. This solvent dependence indicates new possibilities to improve metastability toward further applications.

    7. Coordination Chemistry

      Evolution of the Coordination-Sphere Symmetry in Copper(II), Nickel(II), and Zinc(II) Complexes with N,N′-Double-Armed Diaza-Crown Ethers: Experimental and Theoretical Approaches

      Katalin Selmeczi, Jean-Pierre Joly, Mustapha Allali, Violeta Yeguas, Bernard Henry and Manuel Ruiz-Lopez

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402432

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      Symmetric versus asymmetric octahedral coordination geometry changes were observed for Cu2+, Ni2+, and Zn2+ complexes of a N,N′-triazolyl-biarmed diaza[18]crown-6 macrocycle. Quantum chemical calculations at the DFT level confirmed these observations and allowed us to interpret them in terms of covalent or noncovalent metal–ligand interactions.

    8. Solid-State Structures

      New Lithium-Containing Pnictides with 1-D Infinite Chains of Supertetrahedral Clusters: Synthesis, Crystal and Electronic Structure of Ba4Li2Cd3Pn6 (Pn = P, As and Sb)

      Julien P. A. Makongo, Tae-Soo You, Hua He, Nian-Tzu Suen and Svilen Bobev

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402434

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      Three new Zintl phases have been synthesized for the first time, and their crystal structures have been established by single-crystal X-ray diffraction. They crystallize with their own-structure type in the orthorhombic space group Cmcm (Pearson code oC60) and their crystal structure is based on one-dimensional infinite chains of supertetrahedral clusters, [Cd4Pn10].

    9. Catalytic Networks

      Two-Dimensional {Co3+–Co2+} and {Fe3+–Co2+} Networks and Their Heterogeneous Catalytic Activities

      Sumit Srivastava, Manvender Singh Dagur and Rajeev Gupta

      Article first published online: 29 AUG 2014 | DOI: 10.1002/ejic.201402375

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      Reusable two-dimensional {Co3+–Co2+} and {Fe3+–Co2+} networks heterogeneously catalyze Knoevenagel condensation and cyanation reactions of assorted aldehydes owing to the kinetic lability and Lewis acidity of the secondary Co2+ ions.

  2. Short Communications

    1. Magnetic Anisotropy in Dy Complexes

      An Ionic Dysprosium Complex Made of a Hexanuclear Dy6 Cationic Cluster and a Mononuclear Dy Anionic Unit

      Jean-Pierre Costes and Carine Duhayon

      Article first published online: 27 AUG 2014 | DOI: 10.1002/ejic.201402622

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      A novel hydrazide ligand allows the preparation of an ionic species made of a cationic hexanuclear Dy6 cluster and an anionic mononuclear Dy unit, which corresponds to the 2,4M6–1 + 1(0) motif observed for the first time with Ln ions.

    2. Ruthenium Sensitizers

      Efficient Ruthenium Sensitizer with a Terpyridine Ligand Having a Hexylthiophene Unit for Dye-Sensitized Solar Cells: Effects of the Substituent Position on the Solar Cell Performance

      Hironobu Ozawa, Takahiro Kuroda, Shohei Harada and Hironori Arakawa

      Article first published online: 27 AUG 2014 | DOI: 10.1002/ejic.201402530

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      A novel ruthenium sensitizer with a terpyridine ligand having a hexylthiophene unit at the 4-position (TUS-38) has been synthesized, and the dye-sensitized solar cell with TUS-38 showed a 10.6 % conversion efficiency under AM 1.5 (100 mW/cm2) irradiation.

  3. Microreviews

    1. Molecular Catalysts

      Chromophores, Fluorophores and Robust Ancillary Ligands for Molecular Catalysts: 1,3-Bis(2-pyridylimino)isoindolines

      Désirée C. Sauer, Rebecca L. Melen, Matthias Kruck and Lutz H. Gade

      Article first published online: 27 AUG 2014 | DOI: 10.1002/ejic.201402595

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      This microreview focuses on the development of 1,3-bis(2-pyridylimino)isoindolines (BPI) from their synthesis over half a century ago through to their current diverse applications in organic, inorganic and materials chemistry.

  4. Short Communications

    1. Borylene Insertion

      Unprecedented Borylene Insertion into a C–N Bond

      Rajendra S. Ghadwal, Christian J. Schürmann, Felix Engelhardt and Christian Steinmetzger

      Article first published online: 26 AUG 2014 | DOI: 10.1002/ejic.201402750

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      Formation of a boryl-functionalized NHO 6 as a dimer suggests the involvement of a borylene insertion into a C–N bond. The parent borylene (R = H) follows a completely different route in which hydrogen abstraction and intermolecular B–B coupling events seem operative to afford a diborane (7) stabilized by an NHC.

  5. Full Papers

    1. Asymmetric Strecker Reaction

      Chiral MnIII–salalen and –salan Complexes Derived from (S)-Pyrrolidin-2-yl­methanamine and Their Catalytic Activity in the Asymmetric Strecker Reaction

      Pramod Kumar, S. Saravanan, Noor-ul Hasan Khan, Firasat Hussain and Surendra Singh

      Article first published online: 26 AUG 2014 | DOI: 10.1002/ejic.201402548

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      Chiral MnIII–salalen and –salan complexes have been synthesized and used as a catalyst for the asymmetric Strecker reaction. These complexes were characterized by elemental analysis, FTIR and UV/Vis spectroscopy, exact mass determination and single-crystal XRD. The catalyst 9a catalysed the Strecker reactions of a range of substrates with moderate enantioselectivity of the corresponding products.

    2. Heterogeneous Catalysis

      The Nature of the Active Site in Ziegler–Natta Olefin Polymerization Catalysis Systems – A Computational Investigation

      Jugal Kumawat, Virendra Kumar Gupta and Kumar Vanka

      Article first published online: 26 AUG 2014 | DOI: 10.1002/ejic.201402180

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      The nature of the active site in Ziegler–Natta heterogeneous catalysis systems has been explored with density functional theory (DFT). New insights include the understanding that donor coordination to the metal center can lead to an increase in the molecular weight of the polymer. The role of AlEt3 as a possible donor has also been investigated.

  6. Short Communications

    1. Redox-Active Ligands

      Electrochemical Implication of a Hydrogen-Bonded Imidazole on a Redox-Active-Bound Phenolate Group

      Sanae El Ghachtouli, Benedikt Lassalle-Kaiser, Régis Guillot and Ally Aukauloo

      Article first published online: 25 AUG 2014 | DOI: 10.1002/ejic.201402140

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      We report the synthesis and crystallographic structures of zinc complexes with a pentadentate N4O ligand with an imidazole group placed in the ortho position of the phenol group. Furthermore, we describe the influence of the outer-sphere imidazole fragment on the electrochemical behavior of the redox-active-bound phenolate ligand.

  7. Full Papers

    1. Janus-Head NHC Ligands

      Mono- and Hetero-Dinuclear Complexes of Janus-Head NHC Ligands Possessing Backbone Phosphinoyl Groups: the Case of Soft and Hard Metal Centers

      Paresh Kumar Majhi, Spencer C. Serin, Gregor Schnakenburg, Derek P. Gates and Rainer Streubel

      Article first published online: 25 AUG 2014 | DOI: 10.1002/ejic.201402440

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      A family of hybrid ligands composed of hard phosphine oxides and soft N-heterocyclic carbene donor sites have been employed to synthesize [M(cod)Cl(NHCP)] complexes I, which were further converted into the corresponding dicarbonyl complexes in order to study their donor properties. The advantage of backbone phosphinoyl groups was exploited to generate hetero-dinuclear TiIV, RhI complexes 10a,a′.

    2. Polyoxometalates

      Synthesis of Metforminium(2+) Decavanadates – Crystal Structures and Solid-State Characterization

      Irma Sánchez-Lombardo, Eduardo Sánchez-Lara, Aarón Pérez-Benítez, Ángel Mendoza, Sylvain Bernès and Enrique González-Vergara

      Article first published online: 25 AUG 2014 | DOI: 10.1002/ejic.201402277

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      The synthesis, solid-state characterization, and X-ray analyses of three new metforminium(2+) decavanadates are presented. The compositions and stabilities of the three hydrates are strongly modified by the stoichiometry of the reaction and the presence or absence of ammonium cations.

    3. Enzyme Models

      A Nickel-Containing Model System of Acireductone Dioxygenases that Utilizes a C(1)-H Acireductone Substrate

      Caleb J. Allpress and Lisa M. Berreau

      Article first published online: 25 AUG 2014 | DOI: 10.1002/ejic.201402254

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      A NiII complex of a protected C(1)-H acireductone ligand can be deprotected by using NaOCH3 in the presence of O2 to give oxidative aliphatic C–C bond-cleavage products akin to those produced by the NiII-containing acireductone dioxygenase enzyme.

    4. 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.

    5. Multinuclear Complexes

      Tetranuclear Nickel and Cobalt Complexes with an Incomplete Double-Cubane Structure – Homo- and Heterometallic Complexes and Their 1D Coordination Polymers

      Takayuki Nakajima, Keiko Seto, Andreas Scheurer, Bunsho Kure, Takashi Kajiwara, Tomoaki Tanase, Masahiro Mikuriya and Hiroshi Sakiyama

      Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402536

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      Unsymmetrical amine-diol ligands are suitable for the assembly of homo- and heterometallic tetranuclear {M4O6} complexes. 1D coordination polymers are formed by linking the tetranuclear nickel and cobalt complexes with a diol linker ▪▪((<=Author: the size of the graphic for the table of contents had to be reduced for technical reasons))▪▪.

  8. Short Communications

    1. Metal–Organic Frameworks

      Development of a SO3H-Functionalized UiO-66 Metal–Organic Framework by Postsynthetic Modification and Studies of Its Catalytic Activities

      Yi Luan, Nannan Zheng, Yue Qi, Jie Yu and Ge Wang

      Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402509

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      A novel metal–organic framework UiO-66-NH2-derived Brønsted acid catalyst is synthesized by employing a postsynthetic modification strategy under mild conditions. Acetalization and benzimidazole formation are evaluated to demonstrate the high reactivity and selectivity of the nanoscaled UiO-66-NH-RSO3H catalyst.

    2. Crystal Engineering

      Insight into Structure: Function Relationships in a Molecular Spin-Crossover Crystal, from a Related Weakly Cooperative Compound

      Jérôme Elhaïk, Colin A. Kilner and Malcolm A. Halcrow

      Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402623

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      The ClO4 salt of [FeL2]2+ {L = 2,6-bis(3-methylpyrazol-1-yl)pyridine} undergoes very gradual thermal spin-crossover. In contrast, the BF4 salt of the same complex exhibits an abrupt and structured spin-transition, with a complicated structural chemistry. The difference can be attributed to a much larger change in molecular structure between the spin states of the complex in the more cooperative BF4 salt (the weakly cooperative ClO4 salt is pictured).

  9. Full Papers

    1. Metalloenzyme IR Markers

      Mid- and Far-Infrared Marker Bands of the Metal Coordination Sites of the Histidine Side Chains in the Protein Cu,Zn-Superoxide Dismutase

      Bertrand Xerri, Hugo Petitjean, François Dupeyrat, Jean-Pierre Flament, Alain Lorphelin, Claude Vidaud, Catherine Berthomieu and Dorothée Berthomieu

      Article first published online: 21 AUG 2014 | DOI: 10.1002/ejic.201402263

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      The metal–histidine vibrations of the Cu,Zn-superoxide dismutase enzyme are analyzed by mid- and far-infrared difference spectroscopy. The histidine metal–ligand markers are analyzed and assigned from a combination of experimental and computational data. The contributions of the histidine modes are identified through additional data collected and calculated for labelled samples.

  10. Short Communications

    1. Complex Multimetallic Structures

      Combining Cobalt-Assisted Alkyne Cyclotrimerization and Ring Formation through C–H Bond Activation: A “One-Pot” Approach to Complex Multimetallic Structures

      Grzegorz Filipczyk, Alexander Hildebrandt, Ulrike Pfaff, Marcus Korb, Tobias Rüffer and Heinrich Lang

      Article first published online: 20 AUG 2014 | DOI: 10.1002/ejic.201402659

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      A straightforward one-pot synthetic method including cyclotrimerization, C–H activation, and ring formation to novel hexaferrocenylbenzene is discussed. The electrochemical and spectro-electrochemical behavior as well as a mechanism for the formation of the title compound is reported.

  11. Full Papers

    1. Cation Structures

      Protonated Digermane, Distannane, and Diplumbane: Can They Be Made in the Laboratory?

      Yundong Guo, Yanjun Hao, Hui Wang, Yaoming Xie and Henry F. Schaefer III

      Article first published online: 20 AUG 2014 | DOI: 10.1002/ejic.201402510

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      Similarly to C2H7+ and Si2H7+, the Ge2H7+, Sn2H7+, and Pb2H7+ cations are predicted to be energetically favorable to varying degrees, and they appear to have different low-lying structures.

  12. Microreviews

    1. Vapochromic Materials

      Vapochromic Platinum(II) Complexes: Crystal Engineering toward Intelligent Sensing Devices

      Atsushi Kobayashi and Masako Kato

      Article first published online: 20 AUG 2014 | DOI: 10.1002/ejic.201402315

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      Square-planar platinum(II) complexes that exhibit intense changes in luminescence and color based on metallophilic interactions are promising vapochromic materials. In an effort to generate highly sensitive and selective vapor responses, various PtII complexes have been developed by utilizing different intra- and intermolecular interactions.

  13. Full Papers

    1. Inclusion Compounds

      Synthesis, Characterisation and Antiproliferative Studies of Allyl(dicarbonyl)(cyclopentadienyl)molybdenum Complexes and Cyclodextrin Inclusion Compounds

      Susana S. Braga, Vijaya Mokal, Filipe A. Almeida Paz, Martyn Pillinger, Ana F. Branco, Vilma A. Sardão, Cátia V. Diogo, Paulo J. Oliveira, Maria P. M. Marques, Carlos C. Romão and Isabel S. Gonçalves

      Article first published online: 19 AUG 2014 | DOI: 10.1002/ejic.201402540

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      The crystal structure of [(η5-C5H4–COOH)Mo(CO)23-C3H5)] (1) is presented. Both 1 and its phenylalanine derivative were included into β-cyclodextrin (CD) and per-O-methylated β-CD (TRIMEB). Overall, the inclusion contributed to a higher and more specific action on tumour cells, thereby lowering deleterious effects on a healthy myoblast line.

    2. Copper Catalysis

      Tetranuclear Copper(II) Complexes with Macrocyclic and Open-Chain Disiloxane Ligands as Catalyst Precursors for Hydrocarboxylation and Oxidation of Alkanes and 1-Phenylethanol

      Mirela-Fernanda Zaltariov, Mihaela Alexandru, Maria Cazacu, Sergiu Shova, Ghenadie Novitchi, Cyrille Train, Anatolie Dobrov, Marina V. Kirillova, Elisabete C. B. A. Alegria, Armando J. L. Pombeiro and Vladimir B. Arion

      Article first published online: 18 AUG 2014 | DOI: 10.1002/ejic.201402578

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      Two new tetranuclear copper(II) complexes act as homogeneous catalyst precursors for the single-pot hydrocarboxylation of a variety of linear and cyclic Cn (n = 5–8) alkanes into the corresponding Cn+1 carboxylic acids, peroxidative oxidation of cyclohexane, and solvent-free microwave-assisted oxidation of 1-phenylethanol.

  14. Short Communications

    1. Mesoporous Nanoparticles

      Smart Decoration of Mesoporous TiO2 Nanospheres with Noble Metal Alloy Nano­particles into Core–Shell, Yolk–Core–Shell, and Surface-Dispersion Morphologies

      Pengyu Wang, Hiroko Tooriyama, Kazuya Yokoyama, Masataka Ohtani, Haruyasu Asahara, Tomoya Konishi, Nagatoshi Nishiwaki, Masahiko Shimoda, Yoshiyuki Yamashita, Hideki Yoshikawa and Kazuya Kobiro

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402646

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      Au–Pt–Pd@TiO2, Au–Pt@TiO2, and Au@TiO2 mesoporous nanoparticles with core–shell, yolk–core–shell, and surface-dispersion morphologies are synthesized by a solvothermal method in methanol. The alloy cores of the Au–Pt–Pd@TiO2 and Au–Pt@TiO2 yolk–core–shell nanoparticles have Au@Pt–Pd and Au@Pt embedded sub-core–shell structures, respectively.

  15. Microreviews

    1. Metallo Amino Acids

      Redox and Photochemistry of Bis(terpyridine)ruthenium(II) Amino Acids and Their Amide Conjugates – from Understanding to Applications

      Aaron Breivogel, Christoph Kreitner and Katja Heinze

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402466

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      Ruthenium(II) amino acid [Ru(4′-tpy-COOH)(4′-tpy-NH2)]2+ interacts with photons, electrons, and/or protons, to lead to phosphorescence, oxidative and reductive chemistry, acid/base chemistry, proton-coupled electron transfer, photoinduced reductive and oxidative electron transfer, excited-state proton transfer, and energy transfer. Applications include light-emitting electrochemical and dye-sensitized solar cells.

  16. Full Papers

    1. Nanoparticles

      Defining the Structural Parameters of Tri­azole Ligands in the Templated Synthesis of Silver Nanoparticles

      Heba A. Kashmery, Alasdair W. Clark, Ruggero Dondi, Andrew J. Fallows, Paul M. Cullis and Glenn A. Burley

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402593

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      Control of both the size and shape of silver nanoparticles (AgNPs) can be achieved using triazole sugar ligands and the Tollens' reagent [Ag(NH3)2OH] as the silver source. Higher affinity for AgI results in smaller AgNPs, whereas ligands with lower affinity for AgI form larger AgNPs in which the size can be tuned according to the reaction conditions.

    2. Cluster Compounds

      You have full text access to this OnlineOpen article
      Mixed-Metal Oxo Clusters Structurally Derived from Ti6O4(OR)8(OOCR′)8

      Christine Artner, Ayse Koyun, Matthias Czakler and Ulrich Schubert

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402499

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      Fe/Ti, Zn/Ti, Cd/Ti, Ca/Ti, and Sr/Ti mixed-metal oxo clusters were obtained from the reaction of titanium alkoxides with the corresponding metal acetates and methacrylic acid. Their structures can be traced back to that of Ti6O4(OR)8(OOCR′)8 clusters and the structural variations to the different ionic radii and coordination numbers.

    3. Energetic Materials

      Contributions to the Chemistry of N-Methylnitramine: Crystal Structure, Synthesis of Nitrogen-Rich Salts, and Reactions towards 2-Nitro-2-azapropyl Derivatives

      Marcos A. Kettner, Thomas M. Klapötke, Thomas G. Müller and Muhamed Sućeska

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402441

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      The hitherto unknown crystal structure of N-methylnitramine has been determined. Its Mannich product with formaldehyde was treated with 2-nitro-2-azapropyl isocyanate or water to provide products that were characterized as energetic materials and compared to currently used explosives.

    4. 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.

    5. Spin-State Energetics

      Spin-State Energetics of FeII Complexes – The Continuing Voyage Through the Density Functional Minefield

      Benjamin J. Houghton and Robert J. Deeth

      Article first published online: 15 AUG 2014 | DOI: 10.1002/ejic.201402253

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      Calculating the absolute spin-state energies of metal complexes is a challenge for quantum chemistry. Computing trends is easier, but caution is required. Not all functionals perform equally, and even for the good ones, there are generally outliers. Despite significant progress, the “universal functional” remains elusive.

    6. Luminescent Complexes

      o-Oxazolinyl- and o-Thiazolinylphenol as Antennae in Luminescent EuIII and TbIII Complexes

      Sebastiaan Akerboom, E. Tom Hazenberg, Ireen Schrader, Sarah F. Verbeek, Ilpo Mutikainen, Wen Tian Fu and Elisabeth Bouwman

      Article first published online: 14 AUG 2014 | DOI: 10.1002/ejic.201402447

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      Complexes of europium(III) and terbium(III) using the ligands 2-(4,5-dihydro-1,3-oxazol-2-yl)phenol and 2-(4,5-dihydro-1,3-thiazol-2-yl)phenol have been prepared with M/L ratios of 1:3 and 1:4; five of these compounds show bright luminescence upon excitation by near-UV radiation. Crystallisation from DMSO resulted in the formation of CO3-containing octanuclear complexes.

    7. Blue Phosphorescence

      Towards Deep-Blue Phosphorescence: Molecular Design, Synthesis and Theoretical Study of Iridium Complexes with Cyclometalating 2-Phenyl-2H-[1,2,3]tri­azole Ligands

      Yinping Zhao, Jia Tang, Houyu Zhang and Yuguang Ma

      Article first published online: 14 AUG 2014 | DOI: 10.1002/ejic.201402399

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      Two blue-emitting iridium complexes with cyclometalating 2-phenyl-2H-[1,2,3]triazole ligands were synthesized and characterized. The two complexes both show strong deep-blue emission at 77 K, but no emission at room temperature. Calculations suggest that this lack of emmission might be caused by distorted excited state structures of the complexes.

    8. Rhodium

      Synthesis and Characterization of Cationic Synphos-Rhodium Complexes

      Antje Meißner, Hans-Joachim Drexler, Sonja Keller, Carmen Selle, Virginie Ratovelomanana-Vidal and Detlef Heller

      Article first published online: 14 AUG 2014 | DOI: 10.1002/ejic.201402324

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      Several types of cationic Rh complexes generated under reaction conditions starting from the precursor [Rh(Synphos)(diolefin)]BF4 were identified by NMR spectroscopy. Furthermore, six of these species were characterized by X-ray analysis for the first time; this includes the active species [Rh(Synphos)(acetone)2]BF4 as well as deactivating arene complex [Rh(Synphos)(methyl-η6-benzene)]BF4.

    9. Isomerization

      A Differential Scanning Calorimetry and Theoretical Study on the Isomerization of trans-[Co(cyclam)(ONO)2]X (X = PF6, ClO4)

      Abbas Eslami, Nahid Hasani and Saeed Yeganegi

      Article first published online: 14 AUG 2014 | DOI: 10.1002/ejic.201402174

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      The thermal linkage isomerization of the title compounds in the solid state was studied by differential scanning calorimetry (DSC). The observed exothermic DSC peak of the dinitrito isomer was resolved into two peaks that correspond to two isomerization stages. A comparative experimental and DFT study was performed on the thermodynamics and kinetics of the dinitrito to dinitro isomerization.

    10. Diselenaphospholanes

      Reactions of 1,3,2-Diselenaphospholanes with Lewis Acids: Borane and (Pentamethylcyclopentadienyl)rhodium and -iridium Dichloride

      Bernd Wrackmeyer, Elena V. Klimkina and Wolfgang Milius

      Article first published online: 12 AUG 2014 | DOI: 10.1002/ejic.201402486

      Thumbnail image of graphical abstract

      Borane reagents as well as Cp*MCl2 (Cp* = pentamethylcyclopentadienyl; M = Rh, Ir) react with 1,3,2-diselenaphospholanes by the formation of adducts, followed by ring insertion, and finally by exchange.

  17. Short Communications

    1. Macrocyclic Chromophores

      A Macrocyclic 2,2′-Bibenzimidazole Ruthenium(II) Chromophore as a Versatile Building Block for Supramolecular Devices

      Dieter Sorsche and Sven Rau

      Article first published online: 11 AUG 2014 | DOI: 10.1002/ejic.201402609

      Thumbnail image of graphical abstract

      A new pH- and cation-switchable ruthenium(II) chromophore is presented. Owing to the versatility of the macrocyclic 2,2′-bibenzimidazole ligand, the complex presents itself as an attractive new building block for supramolecular arrays.

  18. Full Papers

    1. Uranyl–Organic Frameworks

      Uranyl Ion Complexes with trans-3-(3-Pyridyl)acrylic Acid Including a Uranyl–Copper(II) Heterometallic Framework

      Pierre Thuéry and Jack Harrowfield

      Article first published online: 11 AUG 2014 | DOI: 10.1002/ejic.201402556

      Thumbnail image of graphical abstract

      The heterofunctional pro-ligand trans-3-(3-pyridyl)acrylic acid was used to build a uranyl–copper(II) heterometallic complex, in which the preferential bonding of the two cations reflects hard and soft affinities and which crystallizes as a 3D framework. The crystal structure of a new 1D homometallic uranyl complex with the same ligand is also described.

    2. C–H Activation

      Rationalizing and Disrupting Fluxional Processes in Agostically Stabilized 14-Electron Alkyliridium Hydride Complexes

      Nicholas Phillips, Lucinda Treasure, Nicholas H. Rees, Rémi Tirfoin, John E. McGrady and Simon Aldridge

      Article first published online: 11 AUG 2014 | DOI: 10.1002/ejic.201402516

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      By NMR spectroscopy and DFT methods, the mechanism of fluxional exchange in cationic bis(NHC) IrIII systems with an agostic C–H bond and cis-alkyl/hydride ligands is shown to feature an oxidative pathway. Related nonfluxional systems can be “trapped” by the addition of two-electron donors (L), and their stability to C–H reductive elimination can be tuned through the π-acceptor properties of L.

    3. Solar Cells

      Triphenylamine-Substituted Metalloporphyrins for Solution-Processed Bulk Heterojunction Solar Cells: The Effect of the Central Metal Ion on Device Performance

      Yunan Zhang, Shitong Zhang, Liang Yao, Leiqiang Qin, Li Nian, Zengqi Xie, Bing Yang, Linlin Liu and Yuguang Ma

      Article first published online: 11 AUG 2014 | DOI: 10.1002/ejic.201402427

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      Porphyrins with enhanced solubility and intermolecular interactions have been developed by incorporating the flexible and strong electron-donating triphenylamine substituent. Furthermore, different metal(II) ions have been introduced to the porphyrin and applied in organic photovoltaics to study the effects of the central metal ions on device performance.

    4. Solid-Phase Synthesis

      Mechanochemical Synthesis of SiO44–-Substituted Hydroxyapatite, Part II – Reaction Mechanism, Structure, and Substitution Limit

      Natalya Bulina, Marina Chaikina, Andrey Andreev, Olga Lapina, Arcady Ishchenko, Igor Prosanov, Konstantin Gerasimov and Leonid Solovyov

      Article first published online: 11 AUG 2014 | DOI: 10.1002/ejic.201402246

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      Silicate-substituted hydroxyapatite powders containing different amounts of silicon have been synthesized by the mechanochemical method. Several apatite crystal structures that differ by the position of the hydroxy groups have been identified.

    5. 3D Nanoarchitectures

      Synthesis of Urchin-Like FeF2 Nanoarchitectures and Their Conversion into Three-Dimensional Urchin-Like Mesoporous α-Fe2O3 Nanoarchitectures for Methane Activation

      Bing Dong, Hengqiang Zhang, Aiguo Kong, Yingying Kong, Fan Yang and Yongkui Shan

      Article first published online: 11 AUG 2014 | DOI: 10.1002/ejic.201402152

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      Novel urchin-like FeF2 nanoarchitectures have been fabricated by an unconventional nonhomogeneous ionic liquid/diphenyl ether solvothermal method and converted into 3D urchin-like mesoporous α-Fe2O3 nanoarchitectures by solid-state thermal annealing. The α-Fe2O3 nanoarchitectures exhibit good catalytic properties in methane activation reactions.

    6. Solid-Phase Synthesis

      Mechanochemical Synthesis of SiO44–-Substituted Hydroxyapatite, Part I – Kinetics of Interaction between the Components

      Marina Chaikina, Natalya Bulina, Arcady Ishchenko and Igor Prosanov

      Article first published online: 6 AUG 2014 | DOI: 10.1002/ejic.201402247

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      The kinetics of the dry mechanochemical synthesis of hydroxyapatite modified by SiO44– ions is studied. From the first seconds of mechanical activation, the initial Ca(H2PO4)2·H2O partially reacts with CaO to form CaHPO4 (interior of the nanoparticles); the nanoparticle shell is Ca(H2PO4)2·H2O, and the material located near the nanoparticles is a mechanical mixture of the initial components.

    7. Ruthenium Complexes

      [Ge(H)(2-C6H4PPh2)3] as Ligand Precursor at Ruthenium: Formation and Reactivity of [Ru(Cl){Ge(2-C6H4PPh2)3}]

      Roy Herrmann, Thomas Braun and Stefan Mebs

      Article first published online: 6 AUG 2014 | DOI: 10.1002/ejic.201402256

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      The ruthenium complex [Ru(Cl){Ge(2-C6H4PPh2)3}] can be converted into the dihydrogen complex [Ru{Ge(2-C6H4PPh2)3}(H)(H2)] on treatment with KH in a dihydrogen atmosphere. A reaction of [Ru{Ge(2-C6H4PPh2)3}(H)(H2)] with hydrazine led to its catalytic disproportionation to give ammonia and the ammonia complex [Ru{Ge(2-C6H4PPh2)3}(H)(NH3)].

  19. Short Communications

    1. Cu–Radical-Supported Oxidation

      Copper(II)-Coordinated α-Azophenols: Effect of the Metal-Ion Geometry on Phenoxyl/Phenolate Oxidation Potential and Reactivity

      Amélie Kochem, Alexandre Carrillo, Christian Philouze, Maurice van Gastel, Amaury du Moulinet d'Hardemare and Fabrice Thomas

      Article first published online: 6 AUG 2014 | DOI: 10.1002/ejic.201402312

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      Tetrahedral distortion at the metal ion in a copper(II) complex containing tridentate ligands with a (Nquinoline,Nazo,Ophenol) donor set is tuned by the α-quinoline substituent. The CuII–phenoxyl radical species oxidizes benzyl alcohol at rate constants that are essentially independent of the distortion at the metal center.

  20. Full Papers

    1. Sila-Galbanones

      Sila-α-galbanone and Analogues: Synthesis and Olfactory Characterization of Silicon-Containing Derivatives of the Galbanum Odorant α-Galbanone

      Steffen Dörrich, Anna Ulmer, Christoph Mahler, Christian Burschka, Johannes A. Baus, Reinhold Tacke, An Chai, Changming Ding, Yue Zou, Gerhard Brunner, Andreas Goeke and Philip Kraft

      Article first published online: 5 AUG 2014 | DOI: 10.1002/ejic.201402597

      Thumbnail image of graphical abstract

      Sila-α-galbanone, sila-α-spirogalbanone, and sila-nor-α-galbanone (sila-analogues of α-galbanone, α-spirogalbanone, and nor-α-galbanone) were synthesized starting from Me2SiCl2, (CH2=CH)2SiCl2, and Me2(CH2=CH)SiCl, respectively. These sila-analogues proved to be less volatile and thus more tenacious than the parent carbon compounds while also providing insight into structure–odor correlations.

    2. Pincer Complexes

      Microwave-Assisted C–C and C–S Couplings Catalysed by Organometallic Pd-SCS or Coordination Ni-SNS Pincer Complexes

      Manuel Basauri-Molina, Simón Hernández-Ortega and David Morales-Morales

      Article first published online: 5 AUG 2014 | DOI: 10.1002/ejic.201402571

      Thumbnail image of graphical abstract

      A series of SCS-PdII and SNS-NiII pincer compounds of the type [PdCl{C6H3-2,6-(CH2SR)2}] and [NiCl2{C5H3N-2,6-(CH2SR)2}] {R = tBu, sBu, iBu} were synthesized and used as efficient catalysts in C–C Suzuki–Miyaura and C–S thiolation cross-coupling reactions.

    3. Crystal Growth Study

      Syntheses and Solid-State Structures of Et2SbTeEt and Et2BiTeEt

      Stefan Heimann, Andreas Kuczkowski, Dieter Bläser, Christoph Wölper, Rebekka Haack, Georg Jansen and Stephan Schulz

      Article first published online: 5 AUG 2014 | DOI: 10.1002/ejic.201402471

      Thumbnail image of graphical abstract

      Single crystals of Et2M–TeEt (M = Sb 1, Bi 2) as well as tBu3Sb (3) were grown by using an IR-laser-assisted technique. Compounds 1 and 2 form short intermolecular E···Te interactions in the solid state, which were further investigated with dispersion-corrected density functional theory.

    4. Half-Sandwich Complexes

      (Arene)ruthenium Complexes with Imidazolin-2-imine and Imidazolidin-2-imine Ligands

      Justus Tönnemann, Rosario Scopelliti and Kay Severin

      Article first published online: 5 AUG 2014 | DOI: 10.1002/ejic.201402583

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      (Arene)Ru complexes with imidazolin-2-imine and imidazolidin-2-imine ligands of the general formula [(cymene)RuCl2L] are described. Photochemical activation allows the preparation of complexes in which the imines act as π ligands with tethered imine groups.

    5. Bioinorganic Chemistry

      BOX Ligands in Biomimetic Copper-Mediated Dioxygen Activation: A Hemocyanin Model

      Adam Walli, Sebastian Dechert, Matthias Bauer, Serhiy Demeshko and Franc Meyer

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201402378

      Thumbnail image of graphical abstract

      A series of bis(oxazoline)-copper(I) complexes reversibly bind dioxygen to yield biomimetic μ-η22-peroxo-dicopper(II) species, which represent new functional hemocyanin models. Their kinetics of formation have been studied under cryo conditions, and the complexes have been isolated as surprisingly stable solids. All were investigated by a variety of methods, both in solution and in the solid state.

    6. Pseudorotaxane Synthesis

      Thiacrown Ethers with Oxygen and Sulfur for Coordination: Formation of the Pd and Pt Complexes and Pseudorotaxane with Dialkylammonium

      Hiroyuki Nagai, Yuji Suzaki and Kohtaro Osakada

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201402465

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      Mono-, di-, tri-, and tetrathiacrown ethers form pseudorotaxanes with dialkylammonium salts and transition-metal complexes with palladium(II) and platinum(II). The pseudorotaxanes of di- and tetrathiacrown ethers undergo decomplexation/complexation cycles by competitive metal coordination with PdCl2.

    7. Ate Complexes

      Divalent Transition Metal Silylamide Ate Complexes

      Sonja N. König, David Schneider, Cäcilia Maichle-Mössmer, Benjamin M. Day, Richard A. Layfield and Reiner Anwander

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201402557

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      Donor-free and tetrahydrofuran-coordinated (thf-coordinated) ate complexes of the type (thf)x(AM)M(NR2)3 (x = 0, 1; AM = Li, Na; M = Fe, Cr, Co, Mn) have been synthesized and characterized. The implications of ion size and donor-solvent coordination on the solid-state structures are discussed.

    8. Univalent Gallium Complexes

      σ- or π-Coordination? Complexes of Univalent Gallium Salts with Aromatic Nitrogen Bases

      Martin R. Lichtenthaler, Florian Stahl, Daniel Kratzert, Boumahdi Benkmil, Hermann A. Wegner and Ingo Krossing

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201402360

      Thumbnail image of graphical abstract

      Upon interaction of [Ga(C6H5F)2]+[Al(ORF)4] with pyrazine or 2,6-di-tert-butyl-4-methylpyridine, σ-coordination prevails. Thus, these two aromatic nitrogen bases function as Lewis bases, yielding homoleptic and mixed N-donor complexes or coordination polymers of gallium(I).

  21. Microreviews

    1. Coordination Geometry

      Trigonal Bipyramidal or Square Pyramidal Coordination Geometry? Investigating the Most Potent Geometry for Vanadium Phosphatase Inhibitors

      Debbie C. Crans, Michael L. Tarlton and Craig C. McLauchlan

      Article first published online: 1 AUG 2014 | DOI: 10.1002/ejic.201402306

      Thumbnail image of graphical abstract

      In this microreview, we analyze the five-coordinate geometries (an important factor in phosphoryl group transfer) for a range of VO4X coordination spheres with regard to their structure, considered as square pyramidal or trigonal bipyramidal geometries. We demonstrate that actual differences between the coordination environments are very small and presumably less critical than generally anticipated.

  22. Full Papers

    1. Metal–Organic Frameworks

      One-Pot Multiple Metal–Organic Framework Formation: Concomitant Generation of Structural Isomers or of Drastically Distinct Materials

      Achareeya Cheansirisomboon, Jorge Salinas-Uber, Chiara Massera, Olivier Roubeau, Sujittra Youngme and Patrick Gamez

      Article first published online: 30 JUL 2014 | DOI: 10.1002/ejic.201402475

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      The (solvothermal) reactions to produce MOFs may lead to the simultaneous generation of multiple solid materials, for instance, structural isomers or even radically different compounds.

    2. Palladium Catalysis

      Palladium Nanoparticles Stabilized by ­Glycodendrimers and Their Application in Catalysis

      Sylvain Gatard, Lionel Salmon, Christophe Deraedt, Jaime Ruiz, Didier Astruc and Sandrine Bouquillon

      Article first published online: 30 JUL 2014 | DOI: 10.1002/ejic.201402457

      Thumbnail image of graphical abstract

      Small and monodisperse glycodendrimer-stabilized palladium nanoparticles (PdDSNs) were prepared from low concentrations of metal precursor in the presence of NaBH4. PdDSNs were characterized by transmission electron microscopy (TEM) and their catalytic activities evaluated for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by NaBH4 and for Suzuki–Miyaura C–C coupling.

    3. Ligand Design

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

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

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

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

    4. Iron Phosphonate

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

      Joydeb Goura, Junjie Liu, Paul Goddard and Vadapalli Chandrasekhar

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

      Thumbnail image of graphical abstract

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

    5. Magnetic Properties

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

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

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

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

    6. 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.

    7. 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

      Thumbnail image of graphical abstract

      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.

    8. 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.

    9. 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.

    10. 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

      Thumbnail image of graphical abstract

      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.

    11. 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

      Thumbnail image of graphical abstract

      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.

    12. 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.

    13. 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.

  23. Microreviews

    1. Silver(I) Cyanoximates

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

      Nikolay Gerasimchuk

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

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

    2. Heterometallic Complexes

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

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

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

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

    3. Stimuli-Responsive Materials

      Stimuli-Responsive Dynamic Gold Complexes

      Csaba Jobbágy and Andrea Deák

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

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

  24. 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

      Thumbnail image of graphical abstract

      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.

  25. Full Papers

    1. Selective Crystallization

      Sulfonated Polymethylsiloxane as an Additive for Selective Calcium Oxalate Crystallization

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

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

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

    2. Pincer Ligand Complexes

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

      Yoshihiro Miyake, Kazunari Nakajima, Yu Higuchi and Yoshiaki Nishibayashi

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

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

    3. Macroions

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

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

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

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

    4. Nickel Hydride Electrocatalysts

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

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

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

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

  26. 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.

  27. Full Papers

    1. 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.

    2. 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.

    3. 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

      Thumbnail image of graphical abstract

      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.

    4. 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.

  28. 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.

  29. 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. 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

      Thumbnail image of graphical abstract

      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.

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