Chemistry - A European Journal

Cover image for Vol. 20 Issue 17

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

Editor: Neville Compton, Deputy Editors: Anne Deveson, Elisabeth Roedern

Impact Factor: 5.831

ISI Journal Citation Reports © Ranking: 2012: 21/152 (Chemistry Multidisciplinary)

Online ISSN: 1521-3765

Associated Title(s): Angewandte Chemie International Edition, Chemistry – An Asian Journal, ChemistryOpen, ChemBioChem, ChemCatChem, ChemElectroChem, ChemMedChem, ChemPhysChem, ChemPlusChem, ChemSusChem, European Journal of Inorganic Chemistry, European Journal of Organic Chemistry

  1. Full Papers

    1. Hybrid Materials

      Nanostructured Graphene/TiO2 Hybrids as High-Performance Anodes for Microbial Fuel Cells

      Cui-e Zhao, Wen-Jing Wang, Dong Sun, Dr. Xin Wang, Prof. Jian-Rong Zhang and Prof. Jun-Jie Zhu

      Article first published online: 17 APR 2014 | DOI: 10.1002/chem.201400272

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      Microwave-assisted solvothermal synthesis of TiO2 on graphene led to the assembly of nanostructured G/TiO2 hybrids. The as-synthesized 20 % graphene /TiO2 hybrid exhibited effective bacterial adhesion (see figure) and high power density when used as an anode material in microbial fuel cells.

    2. Biomineral Microstructures

      Solvothermal Transformation of Calcium Oleate Precursor into Large-Sized Highly Ordered Arrays of Ultralong Hydroxyapatite Microtubes

      Dr. Bing-Qiang Lu, Prof. Dr. Ying-Jie Zhu, Feng Chen, Chao Qi, Xin-Yu Zhao and Jing Zhao

      Article first published online: 17 APR 2014 | DOI: 10.1002/chem.201400252

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      By the skin of your teeth: Tooth enamel consists of highly organized arrays of hydroxyapatite (HAP) crystallites. The solvothermal synthesis of millimeter-scale 3D highly ordered arrays of ultralong HAP microtubes inspired by tooth enamel is reported. The ordered HAP microtube arrays form the shell of a core–shell-structured oblate sphere with a core of unordered HAP nanorods and a diameter of 6 mm (see figure).

    3. Natural Products

      Chemical and Toxicological Investigations of a Previously Unknown Poisonous European Mushroom Tricholoma terreum

      Xia Yin, Dr. Tao Feng, Prof. Jian-Hua Shang, Yun-Li Zhao, Fang Wang, Zheng-Hui Li, Ze-Jun Dong, Prof. Dr. Xiao-Dong Luo and Prof. Dr. Ji-Kai Liu

      Article first published online: 17 APR 2014 | DOI: 10.1002/chem.201400226

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      Murderous mushroom identified: A chemical investigation of the fruiting bodies of the mushroom Tricholoma terreum led to the isolation of 15 new triterpenoids including three that possessed a unique 5/6/7 trioxaspiroketal system and three that possessed an unprecedented carbon skeleton (see figure). Two compounds, saponaceolide B and saponaceolide M, were abundantly expressed in the mushroom and displayed acute toxicity, with LD50 values of 88.3 and 63.7 mg kg−1, respectively.

  2. Communications

    1. Polynitrogen Molecules

      All-Nitrogen Analogue of Ozone: Li3N3 Species

      Prof. Dr. Jared K. Olson, Alexander S. Ivanov and Prof. Dr. Alexander I. Boldyrev

      Article first published online: 17 APR 2014 | DOI: 10.1002/chem.201402572

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      Polynitrogen ozone-like molecule: A theoretical prediction of a new polynitrogen molecule is reported. The geometry, electronic, and structural properties of Li3N3 with an unusual N33− kernel were studied using ab initio calculations. Chemical bonding analysis of Li3N3 reveals the same bonding pattern as in ozone molecule (see figure).

    2. Organic Synthesis

      Multicomponent, Flow Diazotization/Mizoroki–Heck Coupling Protocol: Dispelling Myths about Working with Diazonium Salts

      Dr. Kumara S. Nalivela, Michael Tilley, Dr. Michael A. McGuire and Prof. Michael G. Organ

      Article first published online: 17 APR 2014 | DOI: 10.1002/chem.201402092

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      Diazonium salts in flow: A single pass flow diazotization/Mizoroki–Heck protocol has been developed for the production of cinnimoyl and styryl products. The factors that govern aryl diazonium salt stability have been examined in detail leading to the development of a MeOH/DMF co-solvent system in which the diazonium salts can be generated in the presence of all other reaction components and then coupled selectively (see scheme).

  3. Full Papers

    1. Gelators

      A Systematic Study of Peripherally Multiple Aromatic Ester-Functionalized Poly(benzyl ether) Dendrons for the Fabrication of Organogels: Structure–Property Relationships and Thixotropic Property

      Dr. Yu Feng, Zhi-Xiong Liu, Hui Chen, Zhi-Chao Yan, Yan-Mei He, Prof. Dr. Chen-Yang Liu and Prof. Dr. Qing-Hua Fan

      Article first published online: 17 APR 2014 | DOI: 10.1002/chem.201400157

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      Dendritic supragels: A new class of peripherally multiple aromatic ester-functionalized poly(benzyl ether) dendritic organogelators have been synthesized, and their structure–property relationships have been investigated systematically. The second- and third-generation dendrons with dimethyl isophthalates (DMIP) as peripheral groups exhibited the best capability in gelation (see figure).

    2. Density Functional Calculations

      DFT Simulations of Water Adsorption and Activation on Low-Index α-Ga2O3 Surfaces

      Dr. Xin Zhou, Prof. Dr. Emiel J. M. Hensen, Prof. Dr. Rutger A. van Santen and Prof. Dr. Can Li

      Article first published online: 17 APR 2014 | DOI: 10.1002/chem.201400006

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      Beneath the surface: Chemisorption energies of water on different surfaces of α-Ga2O3 do not relate to differences in the respective surface energies or coordinative unsaturation of the surface atoms, but instead with the respective adsorption-induced surface relaxation energies (see figure).

    3. Metal Complexes

      Binuclear trans-Bis(β-iminoaryloxy)palladium(II) Complexes Doubly Linked with Pentamethylene Spacers: Structure-Dependent Flapping Motion and Heterochiral Association Behavior of the Clothespin-Shaped Molecules

      Masaya Naito, Hiroyuki Souda, Hiroshi Koori, Dr. Naruyoshi Komiya and Prof. Takeshi Naota

      Article first published online: 17 APR 2014 | DOI: 10.1002/chem.201305054

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      Flappy complex: Structural, kinetic, and thermodynamic investigation of clothespin-shaped, binuclear trans-bis(β-iminoaryloxy)palladium complexes are consistent with these complexes exhibiting flapping motion and interpenetrative association. The flapping behavior and heterochiral association of anti-1 bearing dilated Z-shaped coordination blades are characteristic of these types of molecules (see graphic).

    4. Luminescence

      Pyrene-Based Bisazolium Salts: From Luminescence Properties to Janus-Type Bis-N-Heterocyclic Carbenes

      Sergio Gonell, Dr. Macarena Poyatos and Prof. Eduardo Peris

      Article first published online: 17 APR 2014 | DOI: 10.1002/chem.201304952

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      Shining examples: A family of luminescent pyrene-based bisazolium salts has been obtained (see figure). The bisazoliums generate Janus-type bis-N-heterocyclic carbenes (bis-NHC), which were coordinated to rhodium and iridium.

    5. Heterogeneous Catalysis

      From the Lindlar Catalyst to Supported Ligand-Modified Palladium Nanoparticles: Selectivity Patterns and Accessibility Constraints in the Continuous-Flow Three-Phase Hydrogenation of Acetylenic Compounds

      Gianvito Vilé, Dr. Neyvis Almora-Barrios, Dr. Sharon Mitchell, Prof. Núria López and Prof. Javier Pérez-Ramírez

      Article first published online: 17 APR 2014 | DOI: 10.1002/chem.201304795

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      Hybrid nanocatalysts: The classical Lindlar and the newly developed NanoSelectTM catalysts are confronted in the semi-hydrogenation of alkynes (see figure). Systematic testing under continuous-flow three-phase conditions, coupled with detailed characterization analyses and molecular simulations, enable the understanding of the structure of the catalysts and the associated activity and selectivity patterns for a wide range of acetylenic compounds.

    6. Electron Transfer

      Functionalization of a Ruthenium–Diacetylide Organometallic Complex as a Next-Generation Push–Pull Chromophore

      Samuel De Sousa, Dr. Laurent Ducasse, Dr. Brice Kauffmann, Prof. Thierry Toupance and Dr. Céline Olivier

      Article first published online: 17 APR 2014 | DOI: 10.1002/chem.201304611

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      The next generation: Asymmetric functionalization of a ruthenium–diacetylide organometallic complex afforded an innovative push–pull structure (see figure; D: donor; A: acceptor) with excellent optoelectronic properties and a good power conversion efficiency rate when it was employed as a photosensitizer in dye-sensitized solar cells.

    7. Mixed-Valent Compounds

      Mixed-Valence Ruthenium Complexes Rotating through a Conformational Robin–Day Continuum

      Matthias Parthey, Dr. Josef B. G. Gluyas, Dr. Mark A. Fox, Prof. Dr. Paul J. Low  and Prof. Dr. Martin Kaupp

      Article first published online: 16 APR 2014 | DOI: 10.1002/chem.201304947

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      No class? For the first time a combined computational and experimental study demonstrates that mixed-valence complexes may sample regions of localized (class II) and delocalized (class III) character owing to facile conformational motion (see figure). This explains the unusual spectroscopic features for two representative d5/d6 mixed-valence diruthenium complex cations.

  4. Communications

    1. Synthetic Methods

      Synthesis and Elaboration of All-cis-1,2,4,5-Tetrafluoro-3-Phenylcyclohexane: A Polar Cyclohexane Motif

      Dr. Alastair J. Durie, Dr. Tomoya Fujiwara, Rodrigo Cormanich, Prof. Michael Bühl, Prof. Alexandra M. Z. Slawin and Prof. David O'Hagan

      Article first published online: 16 APR 2014 | DOI: 10.1002/chem.201400354

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      A stereocontrolled synthesis of all-cis-1,2,4,5-tetrafluoro-3-phenylcyclohexane is developed as the first functionalised example of this polar cyclohexane motif. The dipolar nature of the cyclohexane ring is explored and the aryl ring is elaborated in different ways to demonstrate its versatility as a molecular building block (see figure).

  5. Full Papers

    1. [2,2]-Paracyclophane

      Phase Transition of [2,2]-Paracyclophane – An End to an Apparently Endless Story

      Dipl.-Chem. Hilke Wolf, Dr. Dirk Leusser, Dr. Mads R. V. Jørgensen, Dr. Regine Herbst-Irmer, Dr. Yu-Sheng Chen, Dr. Ernst-Wilhelm Scheidt, Prof. Dr. Wolfgang Scherer, Prof. Dr. Bo B. Iversen and Prof. Dr. Dietmar Stalke

      Article first published online: 16 APR 2014 | DOI: 10.1002/chem.201304972

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      Low-temperature [2,2]-cyclophane: The hitherto unknown, but long anticipated, low-temperature structure of [2,2]-paracyclophane is described. At temperatures above 45 K, the higher symmetry space group P42/mnm emulates a mirror plane through both ethylene handles, whereas in the low-temperature phase and in the space group Pequation imagen2, the handles are twisted to either side, removing the mirror plane. Heat capacity measurements prove the existence of a λ-type phase transition at 45 K connected with a secondary Cp/T feature at 60 K.

    2. Metal-Free Catalysis

      Hybrid Nanocarbon as a Catalyst for Direct Dehydrogenation of Propane: Formation of an Active and Selective Core–Shell sp2/sp3 Nanocomposite Structure

      Dr. Rui Wang, Xiaoyan Sun, Dr. Bingsen Zhang, Dr. Xiaoying Sun and Prof. Dangsheng Su

      Article first published online: 16 APR 2014 | DOI: 10.1002/chem.201400018

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      Essential imperfections: The evolution of the surface state and catalytic performance of hybrid nanocarbon produced by high-temperature annealing of nanodiamond was investigated. The core–shell sp2/sp3 composite, comprised of a diamond core and a defective, curved graphene shell, exhibits superior catalytic activity that depends strongly on the high concentration of structural defects and high chemical reactivity of ketone-type groups (see figure).

  6. Communications

    1. Self-Assembly

      Dynamic Self-Assembly of Polycationic Clusters Based on Cyclodextrins for pH-Sensitive DNA Nanocondensation and Delivery by Component Design

      Laura Gallego-Yerga, Dr. M. José González-Álvarez, Natalia Mayordomo, Prof. Francisco Santoyo-González, Dr. Juan M. Benito, Prof. Carmen Ortiz Mellet, Prof. Francisco Mendicuti and Prof. José M. García Fernández

      Article first published online: 16 APR 2014 | DOI: 10.1002/chem.201402026

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      Programming self-assembly: pH-Sensitive, hierarchical self-assembly of cyclodextrin-based polycationic clusters and DNA was programmed by the installation of a xylylene moiety at the secondary face of the cyclooligosaccharide. At neutral pH dimer formation facilitates DNA condensation, whereas at acidic pH electrostatic repulsions promote disassembly of the nanocomplexes and DNA release. This can be exploited advantageously in the design of nonviral gene delivery systems (see figure).

  7. Full Papers

    1. Imaging Agents

      Rational Design, Synthesis, and Evaluation of Tetrahydroxamic Acid Chelators for Stable Complexation of Zirconium(IV)

      Dr. François Guérard, Dr. Yong-Sok Lee and Dr. Martin W. Brechbiel

      Article first published online: 16 APR 2014 | DOI: 10.1002/chem.201304115

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      Perfect package: A series of cyclic and acyclic hydroxamic acid based chelators was designed to provide ZrIV complexes with optimal kinetic inertness (see figure). Their evaluation showed that the chelators with the best preorganization provided significantly superior stabilities than desferrioxamine B, the reference compound used in nuclear imaging with 89Zr. The results are rationalized with quantum chemical calculations.

    2. Phenyldiketo Acids

      Long-Range Effects in Anion–π Interactions: Their Crucial Role in the Inhibition Mechanism of Mycobacterium Tuberculosis Malate Synthase

      Antonio Bauzá, Dr. David Quiñonero, Prof. Dr. Pere M. Deyà and Prof. Antonio Frontera

      Article first published online: 16 APR 2014 | DOI: 10.1002/chem.201304995

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      Enhancing anion–π interactions: A combined analysis of the X-ray structures of Mycobacterium tuberculosis malate synthase and computational studies is reported to demonstrate the importance of anion–π interactions in the inhibition mechanism of malate synthase by phenyldiketo acids. The high-level ab initio study demonstrates the prominent role of the Mg2+ ion in the active site, which promotes long-range enhancement of the anion–π interaction (see figure).

    3. Bimetallic Helices

      Multifunctionality in Bimetallic LnIII[WV(CN)8]3− (Ln=Gd, Nd) Coordination Helices: Optical Activity, Luminescence, and Magnetic Coupling

      Szymon Chorazy, Dr. Koji Nakabayashi, Mirosław Arczynski, Dr. Robert Pełka, Prof. Shin-ichi Ohkoshi and Prof. Barbara Sieklucka

      Article first published online: 16 APR 2014 | DOI: 10.1002/chem.201304772

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      Exploring functionalities of cyanido-bridged helices: An unprecedented series of multifunctional molecular materials constructed from one-dimensional chiral GdIII-WV and NdIII-WV helical coordination polymers has been rationally designed, synthesized, and fully characterized (see figure). These materials exhibit natural optical activity in the UV/Vis range, combined with visible or near-infrared luminescence, and cyanido-mediated magnetic coupling.

    4. Green Chemistry

      Cyanoborohydride-Based Ionic Liquids as Green Aerospace Bipropellant Fuels

      Dr. Qinghua Zhang, Dr. Ping Yin, Dr. Jiaheng Zhang and Prof. Dr. Jean'ne M. Shreeve

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201402704

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      It′s not just rocket science! Cyanoborohydride-based ionic liquids exhibit ultra-fast spontaneous combustion on contact with 100 % HNO3. These new ionic liquids have potential applications in bipropellant formulations as environmentally friendly fuels (see scheme).

    5. Electron Density Modeling

      Probing Weak Intermolecular Interactions by using the Invariom Approach: A Comparative Study of s-Tetrazine

      Dr. Yulia V. Nelyubina, Prof. Alexander A. Korlyukov and Prof. Konstantin A. Lyssenko

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201304551

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      Finding strength “in various” weak interactions! A comparative study of chemical bonding in s-tetrazine was carried out to test the performance of a recent invariom approach against a conventional charge density analysis of high-resolution X-ray diffraction data (see figure). The amazing similarity between the intermolecular features thus obtained showed the invariom approximation to now emerge as a fast and convenient way towards reliable description of weak intermolecular interactions.

    6. CO Binding

      The Coordination Chemistry of Pentafluorophenylphosphino Pincer Ligands to Platinum and Palladium

      Dr. Bradley G. Anderson and Prof. John L. Spencer

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201304398

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      Back and forth: The electron-poor P(C6F5)2 donor group was incorporated into the PCP pincer ligand motif to generate a range of poorly donating ligands. Palladium carbonyl complexes of these ligands demonstrated the ability to reversibly bind CO, with the ease of CO displacement increasing with increasing ν(CO) values (see figure). These ligands also displayed a reluctance to undergo metallation on Pt or Pd, which led to the formation of rare examples of cis,trans-dimers.

  8. Communications

    1. Organometallic chemistry

      Lithiated Primary Amine—A New Material for Hydrogen Storage

      Juner Chen, Hui Wu, Prof. Guotao Wu, Prof. Zhitao Xiong, Ruiming Wang, Prof. Hongjun Fan, Dr. Wei Zhou, Bin Liu, Dr. Yongshen Chua, Xiaohua Ju and Prof. Ping Chen

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201402543

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      Endothermic dehydrogenation: Lithiated primary amines, synthesized by ball milling corresponding amines and LiH, exhibit unprecedented endothermic dehydrogenation in the temperature range of 150–250 °C. Li may mediate the dehydrogenation through the α,β-LiH elimination mechanism, creating a more energy favorable pathway for selective H2 release (see figure).

    2. Synthetic Methods

      An Easy Route to (Hetero)arylboronic Acids

      Dr. William Erb, Akila Hellal, Mathieu Albini, Prof. Jacques Rouden and Dr. Jérôme Blanchet

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201402487

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      The simpler the better! A very simple synthesis of (hetero)arylboronic acids is reported (see scheme). This approach features an unprecedented, spontaneous, and fast reactivity of diazonium salts in the presence of diboronic acid, and accommodates a range of functional groups. Consequently, a versatile one-pot borylation of anilines is reported. The radical nature of the reaction mechanism has been investigated.

    3. Water Activation

      Oxidative Addition of Water and Methanol to a Dicationic Trivalent Phosphorus Centre

      Madelyn Qin Yi Tay, Dr. Yunpeng Lu, Dr. Rakesh Ganguly and Dr. Dragoslav Vidović

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201402356

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      Easy and metal free: According to the reaction conditions, activation of equimolar amounts of water by a phosphorus dication could be described as oxidative addition resembling the chemistry of transition metals (see scheme). Fast reaction rates and absence of activations (e.g., boranes) suggested the absence of O[BOND]H bond cleavage prior to the addition.

  9. Full Papers

    1. Aggregation

      Aqueous Self-Assembly and Cation Selectivity of Cobaltabisdicarbollide Dianionic Dumbbells

      Màrius Tarrés, Prof. Clara Viñas, Patricia González-Cardoso, Dr. Mikko M. Hänninen, Prof. Reijo Sillanpää, Vladimír Ďorďovič, Dr. Mariusz Uchman, Prof. Francesc Teixidor and Dr. Pavel Matějíček

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201402193

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      Heavy lifting: Cobaltabisdicarbollide dumbbell-like molecules form aggregates in aqueous solutions. These aggregates are very selective towards alkaline cations and act as cationic exchange platforms with a preference for potassium (see graphic). The dumbbells behave as hook-and-loop fastened crown ethers that are able to release the cation to a signaling unit.

  10. Cover Profiles

    1. A Glutathione-Activated Phthalocyanine-Based Photosensitizer for Photodynamic Therapy

      Dr. Hui He, Prof. Pui-Chi Lo and Prof. Dennis K. P. Ng

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400433

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      The use of “smart” photosensitizers that can only be activated by tumor-associated stimuli can confine the cytotoxic effect at the tumor and spare the normal tissues” Read more about the story behind the cover in the Cover Profile and about the research itself on page ▪▪ ff. (DOI: 10.1002/chem.201400001).

    2. Anionic Bipyridyl Ligands for Applications in Metallasupramolecular Chemistry

      Dr. Mirela Pascu, Mathieu Marmier, Clément Schouwey, Dr. Rosario Scopelliti, Dr. Julian J. Holstein, Dr. Gérard Bricogne and Prof. Kay Severin

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400432

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      We are convinced that clathrochelates are versatile scaffolds for the synthesis of polyfunctional ligands.” Read more about the story behind the cover in the Cover Profile and about the research itself on page ▪▪ ff. (DOI: 10.1002/chem.201400285).

    3. From the Lindlar Catalyst to Supported Ligand-Modified Palladium Nanoparticles: Selectivity Patterns and Accessibility Constraints in the Continuous-Flow Three-Phase Hydrogenation of Acetylenic Compounds

      Gianvito Vilé, Dr. Neyvis Almora-Barrios, Dr. Sharon Mitchell, Prof. Núria López and Prof. Javier Pérez-Ramírez

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400431

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      “Our inspiration was the increasing complexity in the design of alkyne hydrogenation catalysts…” Read more about the story behind the cover in the Cover Profile and about the research itself on page ▪▪ ff. (DOI: 10.1002/chem.201304795).

  11. Communications

    1. Paramagnetic NMR

      A Two-Armed Lanthanoid-Chelating Paramagnetic NMR Probe Linked to Proteins via Thioether Linkages

      Dr. Wei-Min Liu, Dr. Simon P. Skinner, Dr. Monika Timmer, Anneloes Blok, Dr. Mathias A. S. Hass, Dr. Dmitri V. Filippov, Dr. Mark Overhand and Prof. Dr. Marcellus Ubbink

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400257

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      A two-armed probe: α-Bromoacetamides are functionalised in a DOTA-like structure to form a new double-arm paramagnetic probe (see structure). This probe can be site-specifically attached to protein and the ligation products are stable under reducing conditions. This probe creates a new avenue for studying biomolecules using paramagnetic NMR spectroscopy.

    2. Methane Activation

      Thermal Methane Activation by La6O10 Cluster Anions

      Jing-Heng Meng, Xiao-Jiao Deng, Zi-Yu Li, Prof. Dr. Sheng-Gui He and Prof. Dr. Wei-Jun Zheng

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400218

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      Stable and reactive: The La6O10 cluster anion works in thermal methane activation although this cluster is quite stable in terms of obtaining and losing an additional electron (VDE=4.06 eV). The reaction facilitated by the oxygen-centered radical follows a hydrogen-atom transfer mechanism (see figure).

  12. Full Papers

    1. Organic Synthesis

      Oxygenated Metabolites of n-3 Polyunsaturated Fatty Acids as Potential Oxidative Stress Biomarkers: Total Synthesis of 8-F3t-IsoP, 10-F4t-NeuroP and [D4]-10-F4t-NeuroP

      Dr. Alexandre Guy, Dr. Camille Oger, Dr. Johannes Heppekausen, Dr. Cinzia Signorini, Claudio De Felice, Prof. Alois Fürstner, Dr. Thierry Durand and Dr. Jean-Marie Galano

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400380

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      Three for the price of one! Two strategies, Caruso coupling or RCAM, enabled the synthesis of 8-F3t-IsoP and 10-F4t-NeuroP and its deuterated derivative from acetylenic intermediate A (see scheme). Such compounds represent potential biomarkers of neuronal oxidative stress.

    2. Boron-Mediated Synthesis

      Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-coordinate Silicon Alcoholate Complexes

      Dr. Xiansen Li, Dr. Vladimir K. Michaelis , Ta-Chung Ong , Dr. Stacey J. Smith, Prof. Robert G. Griffin  and Prof. Evelyn N. Wang

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400379

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      Mind the van der Waals gap! Well-ordered layered penta-coordinate silicon alcoholate was prepared by a new single-step transesterification mechanism (see scheme), the structure of which was elucidated with one single crystal directly acquired by a novel boron-mediated synthetic route; these complexes are very effective precursors for the facile preparation of high-surface-area amorphous silica powders.

    3. Cyclophanes

      Facile Synthesis and Theoretical Conformation Analysis of a Triazine-Based Double-Decker Rotor Molecule with Three Anthracene Blades

      Max J. Kory, Maike Bergeler, Prof. Markus Reiher and Prof. A. Dieter Schlüter

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400364

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      Two grams of double-decker single crystals in two weeks! New cyclophane can be easily synthesized. It has great potential for more extended structures through anthracene dimerization (see figure).

    4. Energetic Materials

      Dense Energetic Nitraminofurazanes

      Dennis Fischer, Prof. Dr. Thomas M. Klapötke, Marius Reymann and Dr. Jörg Stierstorfer

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400362

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      Safety, performance, and practicality are the key demands on new energetic materials. More than 40 new nitraminobifurazanes were synthesized and characterized with respect to potential energetic use in explosives, propellants and pyrotechnics (see figure).

    5. Supported Catalysis

      Asymmetric Allylation of Ketones and Subsequent Tandem Reactions Catalyzed by a Novel Polymer-Supported Titanium–BINOLate Complex

      Dr. Jagjit Yadav, Dr. Gretchen R. Stanton, Xinyuan Fan, Jerome R. Robinson, Prof. Eric J. Schelter, Prof. Patrick J. Walsh and Prof. Miquel A. Pericas

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400204

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      Two for one with supported BINOL: A new, polystyrene-supported 1,1-binaphthol (BINOL) ligand can be converted into its diisopropoxytitanium derivative in situ and used as a heterogeneous catalyst in the asymmetric allylation of ketones (see scheme). The heterogenized catalytic system is also suitable for tandem asymmetric allylation/epoxidation and allylation/intramolecular Pauson–Khand reactions, affording enantioenriched products with highly increased molecular complexity in a single synthetic operation.

  13. Communications

    1. Synthesis

      Manganese(IV)-Mediated Hydroperoxyarylation of Alkenes with Aryl Hydrazines and Dioxygen from Air

      Stephanie Kindt, Dr. Hannelore Jasch and Prof. Dr. Markus R. Heinrich

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400064

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      The introduction of oxygen into a Meerwein arylation has been achieved with dioxygen from air as oxygen-centered radical scavenger. The slow addition of the aryl hydrazine is key to aryl radical formation through oxidation with manganese dioxide; whereby, hydroperoxides were obtained from activated as well as non-activated alkenes.

    2. Photosensitizers

      A Glutathione-Activated Phthalocyanine-Based Photosensitizer for Photodynamic Therapy

      Dr. Hui He, Prof. Pui-Chi Lo and Prof. Dennis K. P. Ng

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400001

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      Light therapy: Fluorescence emission and reactive oxygen species generation are greatly enhanced in a molecular phthalocyanine-quencher system upon interaction with glutathione (see figure). Its activation has also been demonstrated in vivo.

    3. Supramolecular Flow Chemistry

      Two-Dimensional Assembly Based on Flow Supramolecular Chemistry: Kinetic Control of Molecular Interactions Under Solvent Diffusion

      Prof. Dr. Munenori Numata and Tomohiro Kozawa

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201305006

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      Go with the flow: Self-assembly of porphyrin molecules can be controlled kinetically through a programmed solvent diffusion process in designed microflow spaces (see figure). Temporal solvent structures generated in the microflow were successfully transcribed into molecular architectures.

    4. Biomimetics

      Synthesis and Characterization of NiIIIN3S2 Complexes as Active Site Models for the Oxidized Form of Nickel Superoxide Dismutase

      Chien-Wei Chiang, Yun-Li Chu, Hong-Ling Chen, Ting-Shen Kuo and Prof. Way-Zen Lee

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201304543

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      SOD’s law: Complexes [Ni(H2BARTPP)](ClO4)2 (R=Ph for 1 or iPr for 2; see structure), supported by a pentadentate ligand H2BARTPP, were synthesized and oxidized to form NiIII species having a N3S2 coordination environment to mimic the active site of the oxidized form of NiSOD (NiSODox). DFT calculations reveal that 2+ has an unpaired electron primarily located in the dinline image orbital of the NiIII center.

    5. Aromatic Interactions

      Stabilisation of 2,6-Diarylpyridinium Cation by Through-Space Polar–π Interactions

      Joan Simó Padial, Dr. René de Gelder, Dr. Célia Fonseca Guerra, Prof. Dr. F. Matthias Bickelhaupt and Dr. Jasmin Mecinović

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201304462

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      The through-space polar–π interactions between pyridinium ion and the adjacent aromatic rings in 2,6-diarylpyridines affect the pKa values. Hammett analysis illustrates that the basicity of pyridines correlates well with the sigma values of the substituents at the para position of the flanking aryl rings (see figure).

    6. Synthetic Methods

      On the Frontier Between Nucleophilic Aromatic Substitution and Catalysis

      Martin Pichette Drapeau, Prof. Dr. Thierry Ollevier and Dr. Marc Taillefer

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201304164

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      SNAr or catalysis? A study on the arylation of heteroatom nucleophiles by using activated haloarenes, with or without added metal catalysts, is reported. A discussion concerning the involvement of traces of metals is presented, supported by an unexpected “ligand” effect in the absence of added metal catalysts (see scheme, EWG=electron-withdrawing group).

  14. Full Papers

    1. Ionic Liquids

      A Roadmap to Uranium Ionic Liquids: Anti-Crystal Engineering

      Damla Yaprak, Dr. Eike T. Spielberg, Dr. Tobias Bäcker, Mark Richter, Dr. Bert Mallick, Prof. Dr. Axel Klein and Prof. Dr. Anja-Verena Mudring

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201303333

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      IL effects: Eight tris(N,N-dialkyldithiocarbamato)uranylates (see scheme) are synthesized as salts of 1-butyl-3-methylimidazolium to study the impact of structural variations on the thermal behavior. Room-temperature ionic liquids are obtained with highly asymmetric ligands. Combining low melting points, stable complex formation, and hydrophobicity, these materials qualify for nuclear fuel purification and recovery.

    2. Confined Nanoreactors

      Assembly of a Nanoreactor System with Confined Magnetite Core and Shell for Enhanced Fenton-like Catalysis

      Dr. Tao Zeng, Dr. Xiaole Zhang, Saihua Wang, Yurong Ma, Hongyun Niu and Prof. Yaqi Cai

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201304221

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      An unconventional shell: A novel yolk–shell nanostructure in which both the core and the shell are composed of magnetite (designated as yolk-like Fe3O4@Fe3O4/C) functions as a nanoreactor for the Fenton-like reaction, displaying enhanced catalytic activity compared with conventional solid catalysts (see figure).

    3. Metal–Organic Frameworks

      Incorporating Polyoxometalates into a Porous MOF Greatly Improves Its Selective Adsorption of Cationic Dyes

      Ai-Xue Yan, Dr. Shuang Yao, Prof. Yang-Guang Li, Dr. Zhi-Ming Zhang, Dr. Ying Lu, Dr. Wei-Lin Chen and Prof. En-Bo Wang

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400175

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      The adsorption efficiency and the selective adsorption ability of MIL-101 towards organic dye in aqueous solution were significantly improved by immobilizing polyoxometalates (POMs) into cages of MIL-101. The POM@MIL-101 composites could be readily recycled and reused, and no POM leached during the dye adsorption process (see figure).

    4. Chiral Compounds

      Synthesis, π-Face-Selective Aggregation, and π-Face Chiral Recognition of Configurationally Stable C3-Symmetric Propeller-Chiral Molecules with a π-Core

      Dr. Nozomi Saito, Dr. Ryo Terakawa and Prof. Dr. Masahiko Yamaguchi

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400094

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      Propeller Chirality: C3-symmetric propeller-shaped compounds containing π-cores were synthesized in optically pure states, which possess two distinguishable configurationally stable propeller-chiral π-faces (see figure). π-Face-selective aggregation and π-face chiral recognition were observed in the solid state and in solution.

    5. Helical Structures

      Synthesis and Structures of N-Alkyl-1,13-dimethoxychromeno- [2,3,4-kl]acridinium Salts: The Missing Azaoxa[4]helicenium

      Dr. Thomas Just Sørensen, Dr. Anders Ø. Madsen and Prof. Dr. Bo W. Laursen

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201400082

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      Last but not least! The last of the azaoxa[4]helicenium ions has been synthesised and studied in detail. It is found to be a potent red dye, a stable cation and a structure that can be perturbed depending on the nature of the substituent on the nitrogen atom (see figure).

    6. Strained Polycycles

      A Novel N,P,C Cage Complex Formed by Rearrangement of a Tricyclic Phosphirane Complex: On the Importance of Non-covalent Interactions

      Dr. Vitaly Nesterov, Dr. Arturo Espinosa, Dr. Gregor Schnakenburg and Prof. Dr. Rainer Streubel

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201305061

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      Trityl group in action: Unusual reactivity of the triphenylmethyl group bound to phosphorus leads to intramolecular heterocyclization and formation of strained polycycle I via [3+2] cycloaddition. Complex I rearranges, most probably via transient N-amidinophosphinidene complex II, to give diastereoselectively novel N,P,C cage complex III. The role of non-covalent interactions in II was analyzed theoretically.

    7. Asymmetric Catalysis

      Ureidopeptide-Based Brønsted Bases: Design, Synthesis and Application to the Catalytic Enantioselective Synthesis of β-Amino Nitriles from (Arylsulfonyl)acetonitriles

      Dr. Saioa Diosdado, Dr. Rosa López and Prof. Dr. Claudio Palomo

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201304877

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      Learning from peptides: A concise route for the catalytic enantioselective synthesis of β-amino nitriles has been achieved by using ureidopeptide-based Brønsted bases as catalysts in the Mannich reaction of N-Boc imines and (arylsulfonyl)acetonitriles (see scheme; Boc=tert-butoxycarbonyl, napht=naphthyl, TMS=trimethylsilyl).

    8. Charge Transfer

      A Compact Tetrathiafulvalene–Benzothiadiazole Dyad and Its Highly Symmetrical Charge-Transfer Salt: Ordered Donor π-Stacks Closely Bound to Their Acceptors

      Dr. Yan Geng, Dr. Raphael Pfattner, Antonio Campos, Dr. Jürg Hauser, Prof. Vladimir Laukhin, Dr. Joaquim Puigdollers, Prof. Jaume Veciana, Dr. Marta Mas-Torrent, Prof. Concepció Rovira, Prof. Silvio Decurtins and Dr. Shi-Xia Liu

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201304688

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      Compact donor–acceptor dyad: A compact and planar donor–acceptor molecule 1 comprising tetrathiafulvalene (TTF) and benzothiadiazole (BTD) units has been prepared for investigation of its photoinduced intramolecular charge-transfer process. Chemical oxidation of 1 affords a partially oxidised crystalline charge-transfer (CT) salt {(1)2I3}, and eventually also a fully oxidised compound {1I3}equation imageI2. The former CT salt exhibits a highly symmetrical crystal structure, forming a wire of TTF+0.5 π-stacks with compactly bonded BTD acceptors along its ridge (see graphic). This unique structural feature accounts for its good electrical conductivity of 2 S cm−1 at room temperature.

    9. Fluorophores

      Azacyanines of the Pyrrolopyrrole Series

      Timo Marks, Prof. Dr. Ewald Daltrozzo and Prof. Dr. Andreas Zumbusch

      Article first published online: 15 APR 2014 | DOI: 10.1002/chem.201304235

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      Brightly shining red: The synthesis of pyrrolopyrrole–azacyanines as a new class of long-wavelength-absorbing fluorophores (see figure) is discussed. The boron complexes are especially thermally and photochemically stable fluorescent dyes with strong absorption and fluorescence emissions around 700 nm. The photophysics of the compounds are also discussed and conclusions are drawn about the correlation between molecular structure and optical properties.

    10. Electron Transfer

      Fluorographites (CFx)n Exhibit Improved Heterogeneous Electron-Transfer Rates with Increasing Level of Fluorination: Towards the Sensing of Biomolecules

      Xinyi Chia, Dr. Adriano Ambrosi, Prof. Michal Otyepka, Prof. Radek Zbořil and Prof. Martin Pumera

      Article first published online: 11 APR 2014 | DOI: 10.1002/chem.201402132

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      Need for speed: We have assessed the electroanalytical performances of fluorinated graphites of varying carbon-to-fluorine ratios (see figure). Cyclic voltammetric experiments have shown that among the different fluorographite materials, (CF0.75)n, which possesses the highest F content, yields the fastest heterogeneous electron-transfer rates in [Fe(CN)6]4−/3− and Eu2+/3+ redox probes.

    11. Quintuple Bonds

      Experimental and Theoretical Studies on Arene-Bridged Metal–Metal-Bonded Dimolybdenum Complexes

      Dr. Mario Carrasco, Natalia Curado, Dr. Eleuterio Álvarez, Dr. Celia Maya, Dr. Riccardo Peloso, Prof. Dr. Manuel L. Poveda, Dr. Amor Rodríguez, Prof. Dr. Eliseo Ruiz, Prof. Dr. Santiago Álvarez and Prof. Dr. Ernesto Carmona

      Article first published online: 11 APR 2014 | DOI: 10.1002/chem.201400236

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      Quintuply bound [Mo2{HC(N-2,6-iPr2C6H3)2}2(arene)] complexes (arene=C6H6, C6H5Me, C6H5OMe, p-C6H4Me2, C6H5F, and p-C6H4F2 and Dipp=2,6-iPr2C6H3) have been prepared and structurally characterized by experimental and theoretical methods (see figure). Coordination of the arene to the quintuple MoI–MoI bond results in an effective metal–metal bond order substantially lower than five as a consequence of a strong electronic interaction between δ and δ* dimetal orbitals and the π and π* orbitals of the arene.

    12. Pi Interactions

      Synthesis and Solid-State Structures of a Tetrathiafulvalene-Conjugated Bistetracene

      Masataka Yamashita, Dr. Daiki Kuzuhara, Prof. Dr. Naoki Aratani and Prof. Dr. Hiroko Yamada

      Article first published online: 11 APR 2014 | DOI: 10.1002/chem.201304997

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      High hole mobility: A tetrathiafulvalene (TTF)-conjugated bistetracene was synthesized and characterized in the molecular electronic structures, as well as the packing structures. A variety of crystal packing of compound could be originated from the soft π linkage of TTF unit. The π-stacking structure affords large intermolecular orbital coupling of HOMOs, which is quite beneficial to enhance the charge-carrier mobility (see figure).

  15. Communications

    1. Organic Synthesis

      Zinc-Catalyzed [4+3] Cycloaddition with Concomitant Furan Annulation: Formation of Cyclohepta[b]Furans

      Bo Song, Lian-Hua Li, Xian-Rong Song, Yi-Feng Qiu, Mei-Jin Zhong, Ping-Xin Zhou and Prof. Dr. Yong-Min Liang

      Article first published online: 11 APR 2014 | DOI: 10.1002/chem.201402513

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      Go tandem! A first zinc-catalyzed tandem [4+3] cycloaddition is presented herein. Various substituted cyclohepta[b]furans were synthesized from carbonyl ene–yne and diene in moderate to good yield. Furan rings and seven-membered rings were prepared in one single step (see scheme).

  16. Full Papers

    1. Organic–Inorganic Hybrids

      Integrating 31P DOSY NMR Spectroscopy and Molecular Mechanics as a Powerful Tool for Unraveling the Chemical Structures of Polyoxomolybdate-Based Amphiphilic Nanohybrids in Aqueous Solution

      Assoc. Prof. Pavletta Shestakova , Dr. Gregory Absillis, Dr. Francisco J. Martin-Martinez, Prof. Frank De Proft, Prof. Rudolph Willem and Prof. Tatjana N. Parac-Vogt

      Article first published online: 11 APR 2014 | DOI: 10.1002/chem.201304969

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      Rodlike organic–inorganic hybrids with variable numbers of covalently bound 1,8-octanediphosphonic acid (ODP) and polyoxomolybdate (NH4)6Mo7O24 (POM) units were generated in aqueous solution. The structure, size, and shape of the ODP/POM hybrids as a function of ODP:POM molar ratio were determined by 31P DOSY NMR and molecular mechanics calculations, in combination with 1H, 31P, and 95Mo NMR spectroscopy. Comparison of the calculated (Dcalcd) and experimentally determined diffusion coefficients (Dexptl) led to the most probable ODP/POM hybrid length for each sample composition (see figure).

  17. Communications

    1. Synthetic Methods

      Borylation of Unactivated Aryl Chlorides under Mild Conditions by Using Diisopropylaminoborane as a Borylating Reagent

      Dr. Hélène D. S. Guerrand, Ludovic D. Marciasini, Mélissa Jousseaume, Dr. Michel Vaultier and Dr. Mathieu Pucheault

      Article first published online: 11 APR 2014 | DOI: 10.1002/chem.201304861

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      Salts make the difference: The synthesis of arylboronic ester derivatives from aryl chlorides by using aryl(amino)boranes is described. Palladium-catalyzed coupling between aryl chlorides and diisopropylaminoborane leads to the formation of a C[BOND]B bond under mild conditions. A wide range of substituents, including electron-withdrawing groups, are tolerated (see scheme).

    2. Electrochemistry

      Design of Maleimide-Functionalised Electrodes for Covalent Attachment of Proteins through Free Surface Cysteine Groups

      Emma J. Wright, Dr. Maciej Sosna, Dr. Sally Bloodworth, Prof. Jeremy D. Kilburn and Prof. Philip N. Bartlett

      Article first published online: 10 APR 2014 | DOI: 10.1002/chem.201400246

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      In the mix: A controlled approach to the modification of carbon electrodes with maleimide groups is described for the efficient immobilisation of bovine heart cytochrome c, which is a redox-active model for proteins with free surface cysteine residues (see figure; PG=protecting group, GC=glassy carbon).

  18. Full Papers

    1. NMR Spectroscopy

      You have full text access to this OnlineOpen article
      Fast Proton Exchange in Histidine: Measurement of Rate Constants through Indirect Detection by NMR Spectroscopy

      Akansha Ashvani Sehgal, Dr. Luminita Duma, Prof. Geoffrey Bodenhausen and Dr. Philippe Pelupessy

      Article first published online: 9 APR 2014 | DOI: 10.1002/chem.201304992

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      Seeking the invisible: The protons attached to the N atoms of histidine in an aqueous solution have hitherto escaped detection owing to the very fast exchange of these protons with the solvent. The exchange rate constants along with the one-bond scalar couplings and chemical shifts of these elusive protons have been determined for a pH range in which the three N nuclei are protonated (see figure).

    2. Drug Delivery

      Anti-cancer Applications of Titanocene-Functionalised Nanostructured Systems: An Insight into Cell Death Mechanisms

      Jesús Ceballos-Torres, Dr. Piroska Virag, Dr. Mihai Cenariu, Dr. Sanjiv Prashar, Prof. Mariano Fajardo, Dr. Eva Fischer-Fodor and Dr. Santiago Gómez-Ruiz

      Article first published online: 8 APR 2014 | DOI: 10.1002/chem.201400300

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      Concealed activity: A series of titanocene-functionalized silica-based materials have been synthesized, characterized, and studied in vitro against human cell lines (see figure). They act as Trojan horses for the incorporation of the titanium active species into cells, leading to much higher quantities of titanium uptake in cells, changing the dynamics of apoptotic morphological and functional changes, and inducing programmed cell death in tumor cell populations.

  19. Communications

    1. Cross-Coupling

      Expedient Iron-Catalyzed Coupling of Alkyl, Benzyl and Allyl Halides with Arylboronic Esters

      Prof. Dr. Robin B. Bedford, Dr. Peter B. Brenner, Dr. Emma Carter, Thomas W. Carvell, Paul M. Cogswell, Prof. Dr. Timothy Gallagher, Prof. Dr. Jeremy N. Harvey, Prof. Dr. Damien M. Murphy, Dr. Emily C. Neeve, Joshua Nunn and Dominic R. Pye

      Article first published online: 8 APR 2014 | DOI: 10.1002/chem.201402174

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      More irons in the fire: Primary and secondary alkyl, benzyl and allyl halides were coupled with arylboronic esters by using very simple iron-based catalysts. These were either adducts of inexpensive and widely available diphosphines or, in a large number of cases, simply [Fe(acac)3] with no added co-ligands (see scheme; acac=acetylacetonate). In the former case, preliminary mechanistic studies highlight the likely involvement of low-coordinate iron(I)–phosphine intermediates.

  20. Full Papers

    1. Molecular Motors

      4,4′-Bipyridine as a Unidirectional Switching Unit for a Molecular Pushing Motor

      Christine Kallweit, Prof. Dr. Gebhard Haberhauer and Sascha Woitschetzki

      Article first published online: 8 APR 2014 | DOI: 10.1002/chem.201304166

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      Motor drive: The combination of the intrinsic chirality of a 4,4′-bipyridine with a metal-ion-induced switching principle leads to a metal-ion-induced chirality switch that can also be used as a basic unit for a molecular pushing motor. Rotation around the C[BOND]C bond axis of the bipyridine, which is linked to a cyclic imidazole peptide, leads to switching between P and M isomers (see scheme).

    2. Electrochemistry

      Uniform Decoration of Vanadium Oxide Nanocrystals on Reduced Graphene-Oxide Ball by Aerosol Process for Lithium-Ion Battery Cathode Material

      Seung Ho Choi and Prof. Yun Chan Kang

      Article first published online: 8 APR 2014 | DOI: 10.1002/chem.201400134

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      Graphene-based ball: V2O5-decorated reduced graphene balls and macroporous V2O5 powders were prepared by a spray-pyrolysis process. The V2O5-decorated reduced-graphene balls had higher initial charge and discharge capacities and better cycling and rate performances than the macroporous V2O5 powders (see figure).

    3. Carbohydrates

      Two-Step Functionalization of Oligosaccharides Using Glycosyl Iodide and Trimethylene Oxide and Its Applications to Multivalent Glycoconjugates

      Hsiao-Wu Hsieh, Dr. Ryan A. Davis, Jessica A. Hoch and Prof. Dr. Jacquelyn Gervay-Hague

      Article first published online: 8 APR 2014 | DOI: 10.1002/chem.201400024

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      A two-step methodology for the conjugation of per-O-acetylated oligosaccharides to functionalized linkers, which can be used for various displays, is described. Oligosaccharides were converted to glycosyl iodides and activated with I2, forming reactive donors, which were subsequently trapped with trimethylene oxide (TMO), forming iodopropyl conjugates. Conversion into the corresponding azide followed by copper-catalyzed azide–alkyne cycloaddition afforded multivalent glycoconjugates of Gb3 for further investigation as anti-cancer therapeutics (see scheme).

    4. Phenothiazine-Based Dyes

      Molecular Engineering of Simple Phenothiazine-Based Dyes to Modulate Dye Aggregation, Charge Recombination, and Dye Regeneration in Highly Efficient Dye-Sensitized Solar Cells

      Dr. Yong Hua, Shuai Chang, Jian He, Caishun Zhang, Prof. Jianzhang Zhao, Dr. Tao Chen, Prof. Wai-Yeung Wong, Prof. Wai-Kwok Wong and Dr. Xunjin Zhu

      Article first published online: 8 APR 2014 | DOI: 10.1002/chem.201304897

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      Shape sensitivity: A solar cell sensitized with a phenothiazine-based dye containing a bithiophene unit (TTP) as the electron donor has a high power conversion efficiency (PCE) of 7.87 %, whereas a related dye containing an ethylenedioxythiophene and thiophene unit (ETP) and that containing an ethylenedioxythiophene dimer (EEP) have much lower PCE values. The photovoltaic performance is sensitive to structural modifications (see picture).

    5. Prebiotic Chemistry

      Unearthing the Mechanism of Prebiotic Nitrile Bond Reduction in Hydrogen Cyanide through a Curious Association of Two Molecular Radical Anions

      Ambar Banerjee, Gaurab Ganguly, Ravi Tripathi, Dr. Nisanth N. Nair and Dr. Ankan Paul

      Article first published online: 8 APR 2014 | DOI: 10.1002/chem.201304627

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      Where like attracts like: Theoretical studies show that the prebiotic reduction of the nitrile bond in HCN is initiated through the formation of a dipole anion (see figure, PCET=proton-coupled electron transfer). This is followed by association of two doublet [HCN] radical anions leading to the formation of a transient singlet dianion species. Subsequently, a proton-coupled electron transfer occurs within the dianion electron trap effecting the reduction of HCN.

    6. Photophysics

      A Theoretical Investigation into the Luminescent Properties of d8-Transition-Metal Complexes with Tetradentate Schiff Base Ligands

      Dr. Glenna So Ming Tong, Dr. Pui Keong Chow, Dr. Wai-Pong To, Prof. Wai-Ming Kwok and Prof. Chi-Ming Che

      Article first published online: 8 APR 2014 | DOI: 10.1002/chem.201304375

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      Low, but not ignored: Low-frequency normal modes are usually not considered to be important in determining nonradiative decay rates because they are not effective energy acceptors. The importance of these low-frequency normal modes in estimating knr by using a convolution approach is highlighted (see figure).

    7. C[BOND]H Activation

      Substrate-Dependent H/D Kinetic Isotope Effects and the Role of the Di(μ-oxo)diiron(IV) Core in Soluble Methane Monooxygenase: A Theoretical Study

      Binh Khanh Mai and Yongho Kim

      Article first published online: 8 APR 2014 | DOI: 10.1002/chem.201303466

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      Very large kinetic isotope effects (KIEs) were observed for the H-transfer of CH4 and CH3CN in the C[BOND]H activation by soluble methane monooxygenase; however, a relatively small KIE was observed for CH3NO2. Variational transition-state-theory calculations including tunneling revealed that the diverse KIE values originated mostly from substrate-dependent tunneling (see figure). The H-transfer dynamics and the role of the diiron core depend on the substrates.

    8. Dehydrogenation

      Metal–Ligand Cooperation on a Diruthenium Platform: Selective Imine Formation through Acceptorless Dehydrogenative Coupling of Alcohols with Amines

      Biswajit Saha, S. M. Wahidur Rahaman, Prosenjit Daw, Gargi Sengupta and Prof. Jitendra K. Bera

      Article first published online: 8 APR 2014 | DOI: 10.1002/chem.201304403

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      Ligand lends a hand: Metal–hydroxy/hydroxide and metal–metal cooperation is demonstrated for acceptorless dehydrogenation of alcohols to give aldehydes. The ligand architecture ensures rapid extrusion of the aldehyde from the metal core, resulting in the formation of the corresponding imine as the sole coupled product with amines (see scheme; DABCO=1,4-diazabicyclo[2.2.2]octane).

    9. Solar Cells

      Performance Enhancement of Bulk Heterojunction Solar Cells with Direct Growth of CdS-Cluster-Decorated Graphene Nanosheets

      Kai Yuan, Prof. Dr. Lie Chen, Dr. Licheng Tan and Prof. Dr. Yiwang Chen

      Article first published online: 7 APR 2014 | DOI: 10.1002/chem.201400119

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      Two-dimensional exciton dissociation centers were fabricated in situ. By incorporating these centers into active layers (see figure, ITO=indium tin oxide, GO=graphene oxide), exciton dissociation and separation was dramatically improved with remarkably enhanced collecting and transporting efficiency of photoinduced electrons and holes, and thus elevated device performance.

    10. Organic Synthesis

      You have full text access to this OnlineOpen article
      Carbamoyl Radical-Mediated Synthesis and Semipinacol Rearrangement of β-Lactam Diols

      Dr. Marie Betou, Dr. Louise Male, Prof. Jonathan W. Steed and Dr. Richard S. Grainger

      Article first published online: 7 APR 2014 | DOI: 10.1002/chem.201304982

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      Let the phosphorane take the strain: Cyclic activation is key to achieving high yields in the semipinacol rearrangement of fused β-lactam diols to keto-bridged bicyclic amides, with cyclic phosphoranes proving particularly effective. Functionalized β-lactams are readily obtained through a tandem 4-exo-trig carbamoyl radical cyclization, with the dithiocarbamate group providing the synthetic handle for diol incorporation (see scheme).

    11. Graphene

      Cytotoxicity Profile of Highly Hydrogenated Graphene

      Elaine Lay Khim Chng, Prof. Zdeněk Sofer and Prof. Martin Pumera

      Article first published online: 7 APR 2014 | DOI: 10.1002/chem.201304911

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      Toxic avenger: Highly hydrogenated graphene (HHG) was discovered to be cytotoxic towards A549 cells across a wide range of concentrations tested, and at the same time it is much more cytotoxic than graphene oxide (see figure). It is hypothesized that the hydrophobic nature as a result of the saturated carbon bonds in HHG plays a key role in its cytotoxicity.

    12. Ring-Opening Polymerisation

      Chiral (1,2)-Diphenylethylene-Salen Complexes of Triel Metals: Coordination Patterns and Mechanistic Considerations in the Isoselective ROP of Lactide

      Nicolas Maudoux, Dr. Thierry Roisnel, Dr. Vincent Dorcet, Prof. Dr. Jean-François Carpentier and Dr. Yann Sarazin

      Article first published online: 7 APR 2014 | DOI: 10.1002/chem.201304788

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      Class act: A new range of monometallic chiral salen–aluminium complexes based on a less-classical chiral backbone has been developed. These constitute efficient precatalysts for the isoselective ring-opening polymerisation of racemic lactide. According to chain-end control, they afford poly(lactide) (PLA) featuring high isotacticity (Pm≈0.80–0.90) in the upper range reported to date (see figure).

    13. Sensors

      CuO–ZnO Micro/Nanoporous Array-Film-Based Chemosensors: New Sensing Properties to H2S

      Zongke Xu, Dr. Guotao Duan , Prof. Yue Li, Dr. Guangqiang Liu, Dr. Hongwen Zhang, Zhengfei Dai and Prof. Weiping Cai

      Article first published online: 7 APR 2014 | DOI: 10.1002/chem.201304722

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      Extra-sensitive films: The CuO–ZnO micro/nanoporous array-film-based chemosensor is fabricated by using a solution-dipping colloidal template. The obtained CuO–ZnO films exhibit a more homogenous structure, higher H2S sensitivity, shorter recovery time, and better selectivity than those of the pure ZnO thin film (see figure).

    14. Self-Assembly

      Synthesis of Mesoporous TiO2/SiO2 Hybrid Films as Efficient Photocatalyst by Polymeric Micelle Assembly

      Yunqi Li, Dr. Bishnu Prasad Bastakoti, Dr. Masataka Imura, Dr. Soo Min Hwang, Dr. Ziqi Sun, Prof. Jung Ho Kim, Prof. Shi Xue Dou and Prof. Yusuke Yamauchi

      Article first published online: 7 APR 2014 | DOI: 10.1002/chem.201304689

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      Photoactive hybrids: Thermally stable mesoporous TiO2/SiO2 hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle-assembly method. A triblock copolymer, poly(styrene-b-2-vinyl pyridine-b-ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles (see figure).

    15. Influence of the Alkyl Chain Length on the Self-Assembly of Amphiphilic Iron Complexes: An Analysis of X-ray Structures

      Stephan Schlamp, Dr. Peter Thoma and Prof. Dr. Birgit Weber

      Article first published online: 7 APR 2014 | DOI: 10.1002/chem.201304653

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      Looking ahead: Based on the X-ray structures of 15 amphiphilic iron complexes the self-assembly parameter, sap, is introduced that allows to predict when lipid-layer-like structures are observed (see figure). This was used for the crystallisation of a complex with two C22 alkyl chains and can also be applied to other systems.

    16. Sensors

      A Highly Fluorescent Metallosalalen-Based Chiral Cage for Enantioselective Recognition and Sensing

      Jinqiao Dong, Yanfang Zhou, Fangwei Zhang and Prof. Yong Cui

      Article first published online: 7 APR 2014 | DOI: 10.1002/chem.201304606

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      Cage-based chiral sensor: A highly fluorescent coordination cage [Zn8L4I8] can be prepared from enantiopure pyridyl-functionalized metallosalalen units (L). The cage has an amphiphilic helical cavity decorated with chiral NH functionalities and supramolecular interactions generate a 3D polycage network interconnected by pentahedral cages formed by adjacent pentamers (see graphic). The fluorescence of the cage is greatly enhanced either in solution or in the solid state in the presence of enantiomeric saccharides or amines, respectively, with significant enantioselectivity factors.

    17. Electrochemistry

      Ruthenoarenes versus Phenol Derivatives as Axial Linkers for Subporphyrazine Dimers and Trimers

      Dr. Esmeralda Caballero, Dr. Carlos Romero-Nieto, Volker Strauß, Dr. M. Salomé Rodríguez-Morgade, Prof. Dirk M. Guldi, Prof. Jonathan L. Sessler and Prof. Tomás Torres

      Article first published online: 7 APR 2014 | DOI: 10.1002/chem.201304622

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      Making a connection: Cyclopentadienylruthenium π-coordination to the axial phenolic substituent that functions to link individual subporphyrazine (SubPz) subunits in dimers and trimers serves to modify the interactions between the macrocyclic constituents (see figure). The ground and excited states of the SubPz dimers and trimers of this study reflect the nature of the bridging spacer, with the extent of inter-subunit coupling being relatively increased in the case of the ruthenoarene bridged systems.

    18. Photodynamic Therapy

      Silylation Improves the Photodynamic Activity of Tetraphenylporphyrin Derivatives In Vitro and In Vivo

      Prof. Hiroaki Horiuchi, Prof. Masahiro Hosaka, Hiroyuki Mashio, Motoki Terata, Prof. Shintaro Ishida, Prof. Soichiro Kyushin, Prof. Tetsuo Okutsu, Prof. Toshiyuki Takeuchi and Prof. Hiroshi Hiratsuka

      Article first published online: 7 APR 2014 | DOI: 10.1002/chem.201303120

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      Improved photosensitizers: Silylation improves the quantum yield of singlet oxygen sensitization, cellular uptake efficiency, and selective accumulation efficiency in tumors. As a result of these improvements, silylation significantly enhances photodynamic activity (see figure). The results of this work suggest that silylation is a promising strategy for improving photosensitizers for photodynamic therapy.

  21. Communications

    1. Sustainable Synthesis

      The Synthesis of Benzimidazoles and Quinoxalines from Aromatic Diamines and Alcohols by Iridium-Catalyzed Acceptorless Dehydrogenative Alkylation

      Toni Hille, Dr. Torsten Irrgang and Prof. Dr. Rhett Kempe

      Article first published online: 7 APR 2014 | DOI: 10.1002/chem.201400400

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      Aromatic diamines were reacted with alcohols and diols to form benzimidazoles or quinoxalines, respectively (see scheme). In the course of the reactions, water and two equivalents of hydrogen gas were eliminated/liberated. An Ir complex stabilized by a tridentate P^N^P ligand was found to be an efficient catalyst in these reactions.

    2. Green Chemistry

      Chiral Framework with 20-Ring Channels Exhibiting Metal-Activator-Free Photoluminescence

      Dr. Hui-Lin Huang, Zih-Jie Luo, Yu-Chih Kuo and Prof. Sue-Lein Wang

      Article first published online: 7 APR 2014 | DOI: 10.1002/chem.201400249

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      Go green with sucrose! The use of biomass-derived sucrose has unprecedentedly induced the first chiral zinc phosphite structure with 20R channels along with a series of acentric frameworks, unveiling a facile synthesis of chiral nanoporous frameworks. The 20R-channel structures are metal-activator free but display blue-to-white photoluminescence under long UV excitation (see figure).

  22. Full Papers

    1. Cluster Compounds

      Hydroxo-Bridged Dimers of Oxo-Centered Ruthenium(III) Triangle: Synthesis and Spectroscopic and Theoretical Investigations

      Apoorva Upadhyay, Jitendrasingh Rajpurohit, Mukesh Kumar Singh, Richa Dubey, Anant Kumar Srivastava, Prof. Dr. Ashutosh Kumar, Prof. Dr. Gopalan Rajaraman and Prof. Dr. Maheswaran Shanmugam

      Article first published online: 3 APR 2014 | DOI: 10.1002/chem.201304826

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      Ruthenium exchanges better: A one-pot synthetic method has been developed to isolate a trivalent hexameric RuIII cluster, which registers with one of the largest J values (−800.6 cm−1) known to date with a singlet ground state (see figure). The study reveals the importance of having a 4d ion to have a strong exchange interaction even at room temperature. Theoretical calculations shed light on the origin of these strong exchange interactions, which are further supported by detailed NMR studies.

  23. Cover Profiles

    1. Yoctowell Cavities on Magnetic Silica Nanoparticles for pH Stimuli-Responsive Controlled Release of Drug Molecules

      Article first published online: 3 APR 2014 | DOI: 10.1002/chem.201400430

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      In future, designer yoctowells…may provide a useful supramolecular tool and open new avenues in the realm of targeted therapies” Read more about the story behind the cover in the Cover Profile and about the research itself on page ▪▪ ff. (DOI: 10.1002/chem.201400279).

  24. Full Papers

    1. Protein Engineering

      Site-Specific Protection and Dual Labeling of Human Epidermal Growth Factor (hEGF) for Targeting, Imaging, and Cargo Delivery

      Dr. Michael H. Sonntag, Jenny Ibach, Dr. Lidia Nieto, Dr. Peter J. Verveer and Prof. Dr. Luc Brunsveld

      Article first published online: 3 APR 2014 | DOI: 10.1002/chem.201304090

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      A protein expression and dual labeling approach provides access to the human epidermal growth factor (hEGF) with one or two thiol-based ligation sites, thus enabling sequential orthogonal dual hEGF labeling for targeting, imaging, and cargo delivery (see picture). The dual-coupling strategy involving two independent probes for hEGF with full control over location and stoichiometry by using standard thiol chemistry enables the site-specific cargo targeting of epidermal-growth-factor receptor (EGFR)-overexpressing cancer cells with these well-defined hEGF constructs.

    2. Chemosensors

      Highly Selective Detection of Nerve-Agent Simulants with BODIPY Dyes

      Andrea Barba-Bon, Prof. Ana M. Costero, Prof. Salvador Gil, Prof. Anthony Harriman and Dr. Félix Sancenón

      Article first published online: 3 APR 2014 | DOI: 10.1002/chem.201304475

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      For all to see: Two new boron dipyrromethene (BODIPY) derivatives have been synthesized and used as naked-eye colorimetric and fluorescence probes for the detection of nerve-agent simulants (see picture; DCNP=diethylcyanophosphonate, DFP=diisopropylfluorophosphate). Selectivity to nerve-agent simulants versus acidic media has been achieved. Two portable chemosensor kits have been used in real-time monitoring.

    3. Magnetic Nanoparticles

      Yoctowell Cavities on Magnetic Silica Nanoparticles for pH Stimuli-Responsive Controlled Release of Drug Molecules

      Dr. Sheshanath V. Bhosale

      Article first published online: 3 APR 2014 | DOI: 10.1002/chem.201400279

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      Well, well, well: Yoctowell cavities on magnetic silica nanoparticles were used for the encapsulation and release of the drug molecule mitoxantrone (MTZ). MTZ was encapsulated from a bulk solution and then released from the yoctowells using naturally occurring stimuli, that is, pH (7.2–3.0) (see scheme). The sustained release of MTZ from the yoctowells on magnetic particles provides potential for development of a new generation of drug-delivery systems.

    4. Host–Guest Systems

      Systematic Dissection of an Aminopyrrolic Cage Receptor for β-Glucopyranosides Reveals the Essentials for Effective Recognition

      Dr. Oscar Francesconi, Matteo Gentili, Prof. Cristina Nativi, Dr. Ana Ardá, Prof. F. Javier Cañada, Prof. Jesús Jiménez-Barbero and Dr. Stefano Roelens

      Article first published online: 3 APR 2014 | DOI: 10.1002/chem.201400365

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      Comfort is paramount! A set of structures designed for the recognition of glucosides has been obtained by systematically destructuring a tripodal aminopyrrolic cage receptor. A β-glucoside is more effectively recognized by an adaptive cleft than by a preorganized cage, if a more comfortable fit can be achieved (see picture).

    5. Materials Design

      Quaternary Sulfide Ba6Zn6ZrS14: Synthesis, Crystal Structure, Band Structure, and Multiband Physical Properties

      Xian Zhang, Jianqiao He, Wei Chen, Ketian Zhang, Prof. Chong Zheng, Prof. Dr. Junliang Sun, Fuhui Liao, Prof. Dr. Jianhua Lin and Prof. Dr. Fuqiang Huang 

      Article first published online: 3 APR 2014 | DOI: 10.1002/chem.201304525

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      Bandgap engineering: ZnS- and ZrS-based building blocks were combined to construct multicomponent material Ba6Zn6ZrS14, which features two types of one-dimensional chains parallel to the c axis and shows a much more complex absorption character than simple ZnS and ZrS2 materials, with three optical absorption edges around 1.78, 2.50, and 2.65 eV (see figure).

    6. Alkaloid Synthesis

      Catalytic Asymmetric Assembly of Octahydroindolones: Divergent Synthesis of Lycorine-type Amaryllidaceae Alkaloids (+)-α-Lycorane and (+)-Lycorine

      Zhongwen Sun, Mingtao Zhou, Xiang Li, Xueling Meng, Fangzhi Peng, Prof. Hongbin Zhang and Prof. Zhihui Shao

      Article first published online: 3 APR 2014 | DOI: 10.1002/chem.201400178

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      Octahydroindolone motifs are constructed diastereo- and enantioselectively through a catalytic enantioselective 1,4-conjugate addition of nitro dienynes, followed by a TsOH-catalyzed cascade reaction. This methodology has been applied in the divergent enantioselective synthesis of perhydroindole alkaloids, as exemplified by lycorine-type Amaryllidaceae alkaloids (+)-α-lycorane and (+)-lycorine (see scheme), from a common intermediate by using a highly concise synthetic route.

    7. Host–Guest Systems

      Synthesis and Electronic Properties of 1,2-Hemisquarimines and Their Encapsulation in a Cucurbit[7]uril Host

      Christian C. De Filippo, Dr. Hao Tang, Luca Ravotto, Dr. Giacomo Bergamini, Dr. Patrizio Salice, Dr. Miriam Mba, Prof. Paola Ceroni, Prof. Elena Galoppini and Prof. Michele Maggini

      Article first published online: 3 APR 2014 | DOI: 10.1002/chem.201400039

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      Be square! 1,2-Hemiquarimines (see figure), with one unsubstituted or derivatized phenylimine group, can be synthesized from the corresponding 1,2-squaraine. The interesting photophysical and redox characteristics of these dyes make them useful candidates for charge transfer and sensitization studies.

    8. VOC Capture

      Enhanced Formaldehyde-Vapor Adsorption Capacity of Polymeric Amine-Incorporated Aminosilicas

      Dr. Akihiro Nomura and Prof. Dr. Christopher W. Jones

      Article first published online: 3 APR 2014 | DOI: 10.1002/chem.201304954

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      Volatile organic compounds: Polymeric amine-incorporated porous silicas (aminosilicas) adsorb toxic airborne formaldehyde. The adsorption capacity increases along with the amine loadings until the polymeric amines completely fill the silica pores, achieving four times higher adsorption capacity than the previous aminosilicas constructed from aminosilanes (see figure).

  25. Communications

    1. Organic Synthesis

      Isocyanide-Based Multicomponent Reactions: Concise Synthesis of Spirocyclic Oxindoles with Molecular Complexity by Using a [1,5]-Hydrogen Shift as the Key Step

      Shikuan Su, Chunju Li, Prof. Dr. Xueshun Jia and Prof. Dr. Jian Li

      Article first published online: 2 APR 2014 | DOI: 10.1002/chem.201402576

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      Shift your perspective! An unprecedented cascade reaction, under mild conditions, involving a double Michael addition, double cyclization, and double [1,5]-hydrogen shift, followed by group migration is disclosed. This reaction offers a fast and straightforward approach to unusual polycyclic spirooxindoles (see scheme).

  26. Full Papers

    1. Polyoxometalates

      Synthesis of α-Dawson-Type Silicotungstate [α-Si2W18O62]8− and Protonation and Deprotonation Inside the Aperture through Intramolecular Hydrogen Bonds

      Takuo Minato, Dr. Kosuke Suzuki, Dr. Keigo Kamata and Prof. Dr. Noritaka Mizuno

      Article first published online: 2 APR 2014 | DOI: 10.1002/chem.201400390

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      Give and take: An inorganic anionic cage, TBA8[α-Si2W18O62] (TBA=tetra- n-butylammonium), was successfully synthesized by using the precursor TBA4H6[α-SiW9O34] under mild conditions and in an organic solvent in which it was soluble. The aperture of TBA8[α-Si2W18O62] was able to be protonated and deprotonated by means of intramolecular hydrogen bonds (see figure).

    2. Supramolecular Chemistry

      Anionic Bipyridyl Ligands for Applications in Metallasupramolecular Chemistry

      Dr. Mirela Pascu, Mathieu Marmier, Clément Schouwey, Dr. Rosario Scopelliti, Dr. Julian J. Holstein, Dr. Gérard Bricogne and Prof. Kay Severin

      Article first published online: 2 APR 2014 | DOI: 10.1002/chem.201400285

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      It′s good to be negative: Anionic bipyridyl ligands with dinuclear clathrochelate cores (see scheme) are easily obtained from simple starting materials. These ligands are interesting building blocks for metallasupramolecular chemistry. The utilization of anionic bipyridyl ligands can result in significantly more stable assemblies.

    3. Controlled Release

      Enzyme-Responsive Intracellular-Controlled Release Using Silica Mesoporous Nanoparticles Capped with ε-Poly-L-lysine

      Dr. Laura Mondragón, Núria Mas, Vicente Ferragud, Cristina de la Torre, Dr. Alessandro Agostini, Prof. Ramón Martínez-Máñez, Dr. Félix Sancenón, Prof. Pedro Amorós, Prof. Enrique Pérez-Payá and Dr. Mar Orzáez

      Article first published online: 2 APR 2014 | DOI: 10.1002/chem.201400148

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      Enter the matrix: Two nanodevices capped with polymer ε-poly-L-lysine using different anchoring strategies for controlled delivery are described. The first involves the random formation of urea bonds. The second consists of a specific attachment (see figure, CPT=camptothecin). In vitro release studies demonstrate the enzyme-driven mechanism. Cellular uptake and cell-death induction prove the efficiency of both nanoparticles as platforms for cancer treatment.

  27. Communications

    1. Synthetic Methods

      A Facile Synthesis of Pechmann Dyes

      Prof. Henning Hopf, Prof. Peter G. Jones, Dr. Alina Nicolescu, Prof. Elena Bicu, Dr. Lucian M. Birsa and Dr. Dalila Belei

      Article first published online: 2 APR 2014 | DOI: 10.1002/chem.201400329

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      A facile synthesis of Pechmann dyes has been accomplished by the reaction of substituted N-phenacyl-4-dimethylaminopyridinium halides with dimethyl maleate in the presence of DBU (see scheme). Based on a related 4-DMAP elimination product and an isolated monolactone intermediate a reaction mechanism has been proposed. The scope of this synthetic method is determined by the availability of α-haloaroyl or heteroaroyl derivatives. DBU=1,8-diazabicycloundec-7-ene, DMAP=4-dimethylaminopyridine.

  28. Full Papers

    1. Electrochemistry

      Facile Synthesis of Porous Mn2O3 Nanoplates and Their Electrochemical Behavior as Anode Materials for Lithium Ion Batteries

      Dr. Yanjun Zhang, Dr. Yang Yan, Dr. Xueyun Wang, Dr. Gen Li, Dr. Dingrong Deng, Dr. Li Jiang, Prof. Chunying Shu and Prof. Chunru Wang

      Article first published online: 2 APR 2014 | DOI: 10.1002/chem.201304935

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      Go nano! Porous Mn2O3 nanoplates were prepared by a facile polyol solution method combined with a simple post-annealing process. These porous nanoplates exhibited improved electrochemical performance with excellent cycling stability and good rate capability when used as anode materials for lithium ion batteries (see figure).

    2. Dehydrogenation

      Hydrogen Release from Dialkylamine–Boranes Promoted by Mg and Ca Complexes: A DFT Analysis of the Reaction Mechanism

      Dr. Valeria Butera, Prof. Nino Russo  and Prof. Dr. Emilia Sicilia

      Article first published online: 2 APR 2014 | DOI: 10.1002/chem.201304329

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      Dehydrocoupling of amine–boranes assisted by Mg- and Ca-based complexes was studied by DFT calculations to assess the viability of the pathways of the mechanistic scheme proposed on the basis of experimental evidence and to determine whether different ionic radii and charge densities are responsible for the observed differences in reactivity of Mg and Ca complexes (see scheme). The influence of the steric demand of amine–boranes on the course of the reaction was examined by performing calculations on the dehydrogenation of dimethylamine–borane, pyrrolidine–borane, and diisopropylamine–borane.

    3. Photocatalysis

      Visible-Light-Mediated Addition of α-Aminoalkyl Radicals to [60]Fullerene by Using Photoredox Catalysts

      Dr. Yoshihiro Miyake, Yuya Ashida, Dr. Kazunari Nakajima and Prof. Dr. Yoshiaki Nishibayashi

      Article first published online: 2 APR 2014 | DOI: 10.1002/chem.201304731

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      Let there be light: The functionalization of [60]fullerene by using α-aminoalkyl radicals generated by visible-light-mediated single-electron oxidation of α-silylamines as synthetic intermediates (see picture) has been realized. In these reactions, the introduction of diarylamino groups, which are useful electron donors, was easily achieved.

  29. Communications

    1. Nanostructures

      Coordination Polymer Nanobamboos of {FexIn1−x}-MIL-88B: Induced Formation of a Virtual In-MIL-88B

      Shin Ae Park, Hee Jung Lee, Yea Jin Cho, Sora Choi and Prof. Moonhyun Oh

      Article first published online: 2 APR 2014 | DOI: 10.1002/chem.201304515

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      In bamboo: The preparation of nanobamboos of {FexIn1−x}-MIL-88B is demonstrated. The compositions of the nanobamboos are regulated by altering the amount of metal ions used during their preparation. In addition, the formation of a virtual In-MIL-88B, which is difficult to create in a typical reaction, is induced with the assistance of small amounts of Fe3+ ions.