Chemistry - A European Journal

Cover image for Vol. 20 Issue 19

May 5, 2014

Volume 20, Issue 19

Pages 5513–5839

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    1. You have free access to this content
      Cover Picture: Anionic Bipyridyl Ligands for Applications in Metallasupramolecular Chemistry (Chem. Eur. J. 19/2014) (page 5513)

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

      Version of Record online: 2 MAY 2014 | DOI: 10.1002/chem.201490075

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      Anionic bipyridyl ligands have interesting characteristics for applications in supramolecular coordination chemistry: 1) they are robust, rigid, and relatively long; 2) the lateral size and the solubility of the ligands can be modified by variation of the phenolatodioximato ligand; 3) the Zn-based clathrochelates are luminescent; and 4) it is possible to incorporate diamagnetic or paramagnetic metal ions. For more details see the Full Paper by K. Severin et al. on page 5592 ff.

    2. You have free access to this content
      Back Cover: Synthesis, π-Face-Selective Aggregation, and π-Face Chiral Recognition of Configurationally Stable C3-Symmetric Propeller-Chiral Molecules with a π-Core (Chem. Eur. J. 19/2014) (page 5844)

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

      Version of Record online: 2 MAY 2014 | DOI: 10.1002/chem.201490078

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      Right and left hands are mirror images to each other, and each of them has two distinguishable faces. When two hands lay one upon another, there are several modes of stacking depending on the combination of right/left hands and the two faces. In the same manner, C3-symmetric propeller-shaped compounds possess two distinguishable propeller-chiral π-faces, which can form seven modes of dimeric aggregates. It was found that one of them predominated both in the solid state and in solution. π-Face-selective aggregation and π-face chiral recognition of propeller-chiral molecules are described in the Full Paper by M. Yamaguchi et al. on page 5601 ff.

  2. Cover Profile

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    1. You have free access to this content
      Anionic Bipyridyl Ligands for Applications in Metallasupramolecular Chemistry (page 5517)

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

      Version of Record 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 5592 ff. (DOI: 10.1002/chem.201400285).

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
  4. Corrigendum

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    1. You have free access to this content
      Corrigendum: Enhanced Photocatalytic Hydrogen-Production Performance of Graphene–ZnxCd1−xS Composites by Using an Organic S Source (page 5528)

      Dr. Qin Li, Huan Meng, Prof. Jiaguo Yu, Prof. Wei Xiao, Yingqiu Zheng and Juan Wang

      Version of Record online: 2 MAY 2014 | DOI: 10.1002/chem.201400434

      This article corrects:
  5. News

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
  6. Concept

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    1. Nitroarenes

      Reactions of Nucleophiles with Nitroarenes: Multifacial and Versatile Electrophiles (pages 5536–5545)

      Prof. Dr. Mieczysław Mąkosza

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/chem.201400097

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      The electrophile with many faces: Nucleophiles can react with nitroarenes in many ways: they can add to the ring in positions occupied by hydrogen or halogen atoms to form σH and σX adducts; they can add to the nitrogen or oxygen atoms of the nitro group; they can react through single-electron transfer (see figure). These initial processes are followed by a plethora of further transformations, thus making the reaction of nitroarenes with nucleophiles a rich and versatile toolbox in organic synthesis.

  7. Communications

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    1. Green Chemistry

      Chiral Framework with 20-Ring Channels Exhibiting Metal-Activator-Free Photoluminescence (pages 5546–5549)

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

      Version of Record 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).

    2. Electrochemistry

      Design of Maleimide-Functionalised Electrodes for Covalent Attachment of Proteins through Free Surface Cysteine Groups (pages 5550–5554)

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

      Version of Record 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).

    3. Asymmetric Synthesis

      Coulomb Explosion Imaged Cryptochiral (R,R)-2,3-Dideuterooxirane: Unambiguous Access to the Absolute Configuration of (+)-Glyceraldehyde (pages 5555–5558)

      Dipl.-Chem. Kerstin Zawatzky, Dipl.-Phys. Philipp Herwig, Manfred Grieser, Dr. Oded Heber, Dr. Brandon Jordon-Thaden, Dr. Claude Krantz, Dr. Oldřich Novotný, Dr. Roland Repnow, Prof. Dr. Volker Schurig, Prof. Dr. Dirk Schwalm, Prof. Dr. Zeev Vager, Prof. Dr. Andreas Wolf, Dr. Holger Kreckel and Prof. Dr. Oliver Trapp

      Version of Record online: 6 MAR 2014 | DOI: 10.1002/chem.201400296

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      100 % Absolute: The absolute configuration of (R,R)-2,3-dideuterooxirane, which has been independently determined by Coulomb explosion imaging (CEI), has been unambiguously chemically correlated with the stereochemical key reference (+)-glyceraldehyde. This puts the absolute configuration of D(+)-glyceraldehyde on firm experimental grounds (see scheme).

    4. Nanostructures

      Coordination Polymer Nanobamboos of {FexIn1−x}-MIL-88B: Induced Formation of a Virtual In-MIL-88B (pages 5559–5564)

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

      Version of Record 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.

    5. Synthetic Methods

      A Facile Synthesis of Pechmann Dyes (pages 5565–5568)

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

      Version of Record 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.

    6. Sustainable Synthesis

      The Synthesis of Benzimidazoles and Quinoxalines from Aromatic Diamines and Alcohols by Iridium-Catalyzed Acceptorless Dehydrogenative Alkylation (pages 5569–5572)

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

      Version of Record 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.

    7. Synthetic Methods

      Borylation of Unactivated Aryl Chlorides under Mild Conditions by Using Diisopropylaminoborane as a Borylating Reagent (pages 5573–5579)

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

      Version of Record 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).

    8. Methane Activation

      Thermal Methane Activation by La6O10 Cluster Anions (pages 5580–5583)

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

      Version of Record 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 (vertical electron detachment energy=4.06 eV). The reaction facilitated by the oxygen-centered radical follows a hydrogen-atom transfer mechanism (see figure).

  8. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    1. Imaging Agents

      Rational Design, Synthesis, and Evaluation of Tetrahydroxamic Acid Chelators for Stable Complexation of Zirconium(IV) (pages 5584–5591)

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

      Version of Record 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. Supramolecular Chemistry

      Anionic Bipyridyl Ligands for Applications in Metallasupramolecular Chemistry (pages 5592–5600)

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

      Version of Record 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. Chiral Compounds

      Synthesis, π-Face-Selective Aggregation, and π-Face Chiral Recognition of Configurationally Stable C3-Symmetric Propeller-Chiral Molecules with a π-Core (pages 5601–5607)

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

      Version of Record 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.

    4. Materials Science

      The Mechanism of the One-Step Synthesis of Hollow-Structured Li3VO4 as an Anode for Lithium-Ion Batteries (pages 5608–5612)

      Dr. Yi Shi, Dr. Jie Gao, Prof. Héctor D. Abruña, Prof. Hui-Jun Li, Prof. Hua-Kun Liu, Dr. David Wexler, Prof. Jia-Zhao Wang and Prof. Yuping Wu

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/chem.201400118

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      A feasible method for synthesizing Li3VO4 by a template-free, solution synthesis of single-crystalline microboxes with well-defined non-spherical morphologies is reported (see figure). The formation of hollow structures and the influence of raw materials are presented. The thus-synthesized Li3VO4 exhibited significantly improved electrochemical performance.

    5. Spin-State Ordering

      Spin-State Ordering on One Sub-lattice of a Mononuclear Iron(III) Spin Crossover Complex Exhibiting LIESST and TIESST (pages 5613–5618)

      Dr. Kevin D. Murnaghan, Dr. Chiara Carbonera, Dr. Loic Toupet, Dr. Michael Griffin, Dr. Marinela M. Dîrtu, Dr. Cédric Desplanches, Prof. Dr. Yann Garcia, Prof. Eric Collet, Prof. Jean-François Létard and Dr. Grace G. Morgan

      Version of Record online: 27 MAR 2014 | DOI: 10.1002/chem.201400286

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      Called to order: Real-time single-crystal diffraction is used to follow the dynamics of a symmetry-breaking magnetic and structural phase transition in a mononuclear iron(III) spin crossover complex, which also exhibits a rare LIESST excitation. The thermal symmetry breaking results in spin-state ordering involving just one of the two sub-lattices in the intermediate (INT, see figure) structural phase which is also accessible by LIESST and TIESST (LIESST=Light-induced excited spin-state trapping, TIESST=thermal-induced excited spin-state trapping).

    6. G-Quadruplexes

      Ion-Responsive Hemin–G-Quadruplexes for Switchable DNAzyme and Enzyme Functions (pages 5619–5624)

      Dr. Miguel Angel Aleman-Garcia, Ron Orbach and Prof. Itamar Willner

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/chem.201304702

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      Bound to change: Switchable DNA devices were designed by sequence-programmed nucleic acids that undergo K+-ion-induced self-assembly into G-quadruplexes and the separation of the resulting nanostructures by K+ receptors, such as crown ether or cryptand (see scheme).

    7. Cluster Compounds

      A Microporous Anionic Metal–Organic Framework for Sensing Luminescence of Lanthanide(III) Ions and Selective Absorption of Dyes by Ionic Exchange (pages 5625–5630)

      Dr. Jun-Sheng Qin, Dr. Shu-Ran Zhang, Dr. Dong-Ying Du, Ping Shen, Shao-Juan Bao, Prof. Ya-Qian Lan and Prof. Zhong-Min Su

      Version of Record online: 27 MAR 2014 | DOI: 10.1002/chem.201304480

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      A tetranuclear metal cluster with primitive centered cubic (pcu) topology, IFMC-2, was synthesized as a new anionic metal–organic framework (MOF). The Ln3+-loaded MOF materials were successfully prepared by ion exchange, and the emission spectra indicated that IFMC-2 is suitable for the sensitization of Tb3+ and Dy3+ ions rather than as a Eu3+ and Sm3+ emitter (see picture). Additionally, IFMC-2 exhibits selective absorption toward cationic dyes, which can be gradually released in the presence of NaCl.

    8. Reaction Mechanisms

      On the Mechanism of Bifunctional Squaramide-Catalyzed Organocatalytic Michael Addition: A Protonated Catalyst as an Oxyanion Hole (pages 5631–5639)

      Bianka Kótai, György Kardos, Dr. Andrea Hamza, Dr. Viktor Farkas, Dr. Imre Pápai and Dr. Tibor Soós

      Version of Record online: 27 MAR 2014 | DOI: 10.1002/chem.201304553

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      Finding the path: The mechanism of bifunctional squaramide-promoted Michael addition of prochiral 1,3-dioxo nucleophiles and nitroolefin has been studied on the basis of DFT calculations. Among the investigated mechanistic scenarios, the pathway corresponding to electrophile activation via the protonated amine unit is found to be the most feasible (see figure). For some of the minor stereoisomeric products, alternative pathways are also accessible.

    9. Nanotechnology

      One-Pot Synthesis of Highly Luminescent Carbon Quantum Dots and Their Nontoxic Ingestion by Zebrafish for In Vivo Imaging (pages 5640–5648)

      Yi-Fan Huang, Dr. Xin Zhou, Dr. Rong Zhou, Prof. Hong Zhang, Kai-Bin Kang, Min Zhao, Prof. Yong Peng, Prof. Qiang Wang, Prof. Hao-Li Zhang and Prof. Wen-Yuan Qiu

      Version of Record online: 27 MAR 2014 | DOI: 10.1002/chem.201400011

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      Transformers, quantum dots in disguise! The one-pot, green, and sustainable synthesis and functionalization of highly luminescent carbon quantum dots (CQDs), which can be easily transformed into flexible thin films for future roll-to-roll manufacturing (see scheme; TEOS=tetraethoxysilane, PVA=polyvinyl alcohol), is described. Aqueous CQDs were also applied for the in vivo imaging of zebrafish. The multifunctional CQDs provide a rich pool of tools for optoelectronic and biomedical applications.

    10. Self-Assembly

      Structural Diversity in Multinuclear PdII Assemblies that Show Low-Humidity Proton Conduction (pages 5649–5656)

      Dipak Samanta and Prof. Dr. Partha Sarathi Mukherjee

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/chem.201305075

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      A series of structurally diverse PdII assemblies were synthesized and characterized by controlling the geometry, length, and denticity of the donor. The presence of water clusters and several strong H-bonding interactions between water and NO3 counteranions make these assemblies potential proton-conductive materials that exhibit interesting conductivity even under low-humidity conditions (see scheme).

    11. A New Strategy for Realizing the Conversion of “Homo–Hetero–Homo” Heteroepitaxial Growth in Bi2Te3 and the Thermoelectric Performance (pages 5657–5664)

      Dr. Wei Guo, Jianmin Ma, Jiaqin Yang, Di Li, Qing Qin, Caiying Wei and Prof. Wenjun Zheng

      Version of Record online: 2 APR 2014 | DOI: 10.1002/chem.201304436

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      Subtle interconversions: A low-temperature, easily scalable strategy for synthesizing Bi2Te3 nanostrings is reported. During the process, there is the conversion of homo–hetero–homo heteroepitaxial growth in Bi2Te3 (see picture). The growth of Bi2Te3 nanostrings is a self-assembly process through a wavy competition process generated from Te and Bi3+.

    12. Molecular Dynamics

      Dynamic Molecular Graphs: “Hopping” Structures (pages 5665–5672)

      Prof. Dr. Fernando Cortés-Guzmán, Prof. Dr. Tomas Rocha-Rinza, José Manuel Guevara-Vela, Prof. Dr. Gabriel Cuevas and Prof. Dr. Rosa María Gómez

      Version of Record online: 1 APR 2014 | DOI: 10.1002/chem.201303287

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      Hop to it: The temporal evolution of the molecular structure of [Fe{C(CH2)3}(CO)3] is examined through Born–Oppenheimer molecular dynamics to illustrate the changing behavior of the molecular graph of an electronic system (see figure). Bond paths between the metallic core and C(CH2)3 are uninterruptedly formed and broken, suggesting a “hopping” ligand over the Fe atom.

    13. Aromaticity

      The NICS-XY-Scan: Identification of Local and Global Ring Currents in Multi-Ring Systems (pages 5673–5688)

      Renana Gershoni-Poranne and Prof. Amnon Stanger

      Version of Record online: 27 MAR 2014 | DOI: 10.1002/chem.201304307

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      Assigning aromaticity: Nucleus-independent chemical shift (NICS) scans along the X and Y axes at 1.7 Å above the ring plane reveal local and global ring currents in multi-ring conjugated systems (see figure; blue NICSπZZ (NCS), green NICSZZ, and red NICSπZZ (Sigma-Only)).

    14. Molecular Switch

      Thermal- and Photo-Induced Phase-Transition Behaviors of a Tapered Dendritic Liquid Crystal with Photochromic Azobenzene Mesogens and a Bicyclic Chiral Center (pages 5689–5695)

      Dae-Yoon Kim, Sang-A Lee, Yu-Jin Choi, Dr. Seok-Ho Hwang, Dr. Shiao-Wei Kuo, Dr. Changwoon Nah, Dr. Myong-Hoon Lee and Dr. Kwang-Un Jeong

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/chem.201303924

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      Remote-controlled color: A ribbon-shaped chiral dendritic liquid crystal was newly synthesized, and its thermal and photo-induced phase behaviors were investigated with the combined techniques of the thermal, microscopic, and scattering methods (see figure).

    15. Redox Chemistry

      Unraveling the Mechanism of Water Oxidation Catalyzed by Nonheme Iron Complexes (pages 5696–5707)

      Ferran Acuña-Parés, Zoel Codolà, Dr. Miquel Costas, Dr. Josep M. Luis and Dr. Julio Lloret-Fillol

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/chem.201304367

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      Give me a high 5! The full DFT catalytic cycle for the water oxidation mediated by nonheme iron complexes has allowed the identification of the key steps in this reaction as: 1) FeIV/FeV, and 2) the energy barrier for the O[BOND]O bond formation (see figure). This may have a crucial role in the future development of water oxidation catalysts based on iron.

    16. Cage Compounds

      Optically Active Tetra-tert-butyl-P5-deltacyclene Epimers: Preparation, Spectroscopy, Dynamic Equilibriums, H/D Exchange, and Transition-Metal Complex Chemistry (pages 5708–5720)

      Dr. Lars Rohwer, Dr. Christine Höhn, Prof. Dr. Jochen Autschbach, Prof. Dr. Walter Bauer, Dr. Frank W. Heinemann, Dr. Sergi Huguet Torrell, Dr. Irene Keller, Tatyana E. Shubina, Jacob Steffen and Prof. Dr. Ulrich Zenneck

      Version of Record online: 27 MAR 2014 | DOI: 10.1002/chem.201303821

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      A rigid cage structure combined with a configurationally labile P[BOND]H center generates cage epimers of P5-deltacyclenes. In spite of five competing P atoms and the epimeric nature of the ligand, the [(benzene)RuCl2] unit forms a single complex only by kinetic resolution of the minor ligand epimer (see figure). P5-Deltacyclenes are thus bulky chiral ligands capable of adjusting their stereochemical properties according to the specific requirements of a transition-metal complex fragment.

    17. Solvent Effects

      Charge-Transfer Complex Formation in Gelation: The Role of Solvent Molecules with Different Electron-Donating Capacities (pages 5721–5726)

      Shibaji Basak, Sumantra Bhattacharya, Dr. Ayan Datta and Prof. Arindam Banerjee

      Version of Record online: 27 MAR 2014 | DOI: 10.1002/chem.201303889

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      To gel or not to gel: A naphthalenediimide-based peptide molecule forms a charge-transfer complex with different aromatic hydrocarbon solvents, including toluene, xylenes, and mesitylene, in a particular mixture (chloroform/aromatic hydrocarbon, 4:1). The role of solvents with different electron-donating capacities in the formation of CT complex with different strengths has been established (see figure).

    18. C[BOND]H Activation

      Rhodium-Catalyzed Direct Amination of Arenes with Nitrosobenzenes: A New Route to Diarylamines (pages 5727–5731)

      Dr. Juanjuan Du, Dr. Yaxi Yang, Huijin Feng, Dr. Yuanchao Li and Dr. Bing Zhou

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/chem.201400221

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      A RhIII-catalyzed addition of aryl C[BOND]H bonds to nitrosobenzenes, followed by cleavage of the resulting hydroxylamines in situ, is reported (see scheme). Different directing groups (DG), such as N-based heterocycles and ketoximes, can be used in this C[BOND]H amination process, providing valuable diarylamines in excellent yields. Most importantly, this process provides a new method for attaching arylamine groups to aromatic rings.

    19. N Ligands

      C[BOND]C Coupling of N-Heterocycles at the fac-Re(CO)3 Fragment: Synthesis of Pyridylimidazole and Bipyridine Ligands (pages 5732–5740)

      Maialen Espinal Viguri, Dr. Julio Pérez  and Dr. Lucía Riera

      Version of Record online: 1 APR 2014 | DOI: 10.1002/chem.201400155

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      Re-markable! An unprecedented intramolecular C[BOND]C coupling allows the synthesis of chelate pyridylimidazole complexes from complexes with monodentate pyridine and imidazole ligands. Extension to tris(pyridyl) species afforded 2,2'-bipyridines (see scheme; OTf=trifluoromethanesulfonate).

    20. Fluorescent Sensors

      Development of Fluorescent Film Sensors Based on Electropolymerization for Iron(III) Ion Detection (pages 5741–5745)

      Dr. Peng Li, Changyin Ji, Hongwei Ma, Prof. Ming Zhang and Yunfei Cheng

      Version of Record online: 1 APR 2014 | DOI: 10.1002/chem.201304364

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      Film sensors: Two films made by electropolymerization of electroactive compounds with different metal-chelation sites are made and shown to be highly sensitive and selective fluorescent sensors for Fe3+ ions (see figure; ITO= indium tin oxide).

    21. Coordination Polymers

      Main-Chain Organometallic Microporous Polymers Bearing Triphenylene–Tris(N-Heterocyclic Carbene)–Gold Species: Catalytic Properties (pages 5746–5751)

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

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/chem.201400371

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      Catalytic MOMPs: Two triphenylene-based tris(N-heterocyclic carbene)–gold–acetylide main-chain organometallic microporous polymers (MOMPs) were prepared. The two solids proved to be effective catalysts in the reduction of nitroarenes and in the three-component Strecker reaction for the synthesis of α-aminonitriles (see figure, TMSCN=trimethylsilyl cyanide).

    22. Graphene

      High-Concentration Graphene Dispersions with Minimal Stabilizer: A Scaffold for Enzyme Immobilization for Glucose Oxidation (pages 5752–5761)

      Dr. Zhenyu Sun, Jeevanthi Vivekananthan, Dr. Dmitrii A. Guschin, Dr. Xing Huang, Dr. Volodymyr Kuznetsov, Petra Ebbinghaus, Adnan Sarfraz, Prof. Dr. Martin Muhler and Prof. Dr. Wolfgang Schuhmann

      Version of Record online: 27 MAR 2014 | DOI: 10.1002/chem.201400098

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      Stable relationship: High-yield exfoliation of graphite to pristine graphene nanosheets in water was achieved by using a set of modified acrylate polymers with concentrations of up to approximately 8 g L−1. Redispersing the sediment with water followed by centrifugation allowed graphene dispersions with exceptionally high graphene-to-stabilizer ratios to be produced (see figure).

    23. Nanotechnology

      Freezing Capture of Polymorphic Aggregates of Bolaamphiphilic L-Valine-Based Molecular Hydrogelators (pages 5762–5767)

      Dr. Vicent J. Nebot, Dr. Santiago Díaz-Oltra, Dr. Johan Smets, Susana Fernández Prieto, Dr. Juan F. Miravet and Dr. Beatriu Escuder

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/chem.201400346

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      Gel snapshots: Nanostructured xerogels have been prepared by the freeze-drying of hydrogels and aggregates formed by bolaamphiphilic L-valine derivatives after aging under different conditions. The capture of a diversity of metastable hydrogel nanostructures has been achieved by a combination of molecular flexibility and polymorphism (see photoreel).

    24. Separation Techniques

      Regiospecific Coordination of Re3 Clusters with the Sumanene-Type Hexagons on Endohedral Metallofullerenes and Higher Fullerenes That Provides an Efficient Separation Method (pages 5768–5775)

      Dr. Chia-Hsiang Chen, Dong-Yui Lin and Dr. Wen-Yann Yeh

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/chem.201304356

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      Setting cages free: Reactions of [(μ-H)3Re3(CO)11(NCMe)] with Sc2C2@C80-C2v(5), Sc2@C82-C3v(8), Sc2O@C82-Cs(6), C86-C2(17), and C86-Cs(16) afford face-capping cluster complexes that can be separated by using HPLC (see figure). Carbonylation of each complex releases the corresponding endohedral metallofullerene or higher fullerene in pure form.

    25. Conjugated Materials

      Tuning the Electronic Nature of Mono-Bay Alkynyl–Phenyl-Substituted Perylene Bisimides: Synthesis, Structure, and Photophysical Properties (pages 5776–5786)

      Ruchika Mishra, Dr. Jong Min Lim, Minjung Son, Piyush Panini, Prof. Dr. Dongho Kim and Prof. Dr. Jeyaraman Sankar

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/chem.201400099

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      Single minded: Perylene bisimide derivatives that contain various alkynyl–phenyl substituents at a single-bay position have been synthesized and characterized (see scheme). Detailed studies on the electrochemical and the photophysical properties were explored.

    26. DNA Photochemistry

      Contribution of Cytosine-Containing Cyclobutane Dimers to DNA Damage Produced by Photosensitized Triplet–Triplet Energy Transfer (pages 5787–5794)

      Dr. Thierry Douki, Izabel Bérard, Aude Wack and Sigrid Andrä

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/chem.201303905

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      On the double: The individual quantification of all thymine- and cytosine-containing cyclobutane dimers shows that photosensitized triplet–triplet energy transfer in DNA is not localized on a single isolated base but rather involves at least two bases (see figure; PhSens: photosensitization).

    27. Ruthenium Selenoquinone Complexes

      Selenoquinones Stabilized by Ruthenium(II) Arene Complexes: Synthesis, Structure, and Cytotoxicity (pages 5795–5801)

      Dr. Julien Dubarle-Offner , Catherine M. Clavel, Geoffrey Gontard , Prof. Paul J. Dyson and Dr. Hani Amouri 

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/chem.201304991

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      All in the family: A series of organometallic ruthenium complexes stabilize selenolate, monoselenoquinone, and diselenobenzoquinone entities through π-bonding interactions to a (p-cymene)RuII moiety (see figure). The complexes display moderate cytotoxic properties towards human ovarian cancer cells.

    28. Iron Catalysts

      Well-Defined Iron Complexes as Efficient Catalysts for “Green” Atom-Transfer Radical Polymerization of Styrene, Methyl Methacrylate, and Butyl Acrylate with Low Catalyst Loadings and Catalyst Recycling (pages 5802–5814)

      So-ichiro Nakanishi, Dr. Mitsunobu Kawamura, Hidetomo Kai, Prof. Dr. Ren-Hua Jin, Dr. Yusuke Sunada and Prof. Dr. Hideo Nagashima

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/chem.201304593

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      It's easy being green: Structurally well-defined [(R3TACN)FeX2] complexes realized green atom-transfer radical polymerization by judicious choice of the R group on the N,N,N-trialkylated-1,4,9-triazacyclononane (R3TACN) ligands (see scheme). [{(Cyclopentyl)3TACN}FeBr2] was the best catalyst for controlled polymerization of all three monomers.

    29. Lithium-Ion Batteries

      Iron Fluoride Hollow Porous Microspheres: Facile Solution-Phase Synthesis and Their Application for Li-Ion Battery Cathodes (pages 5815–5820)

      Dr. Jun Liu, Wei Liu, Dr. Shaomin Ji, Yanling Wan, Mingzhe Gu, Huaqi Yin and Prof. Dr. Yichun Zhou

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/chem.201304713

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      Inner space: Uniform iron fluoride hollow microspheres have been synthesized for the first time in a facile and scalable solution-phase route (see figure). These uniform porous and hollow microspheres show a high specific capacity of 210 mA h g−1 at 0.1 C and excellent rate capability (100 mA h g−1 at 1 C) between 1.7–4.5 V versus Li/Li+. In the range of 1.3–4.5 V, a stable capacity of 350 mA h g−1 was achieved at a current of 50 mA g−1.

    30. Metal Complexes

      Interaction between Anions and Cationic Metal Complexes Containing Tridentate Ligands with exo-C[BOND]H Groups: Complex Stability and Hydrogen Bonding (pages 5821–5834)

      Dr. Héctor Martínez-García, Dr. Dolores Morales, Dr. Julio Pérez, Dr. Marcos Puerto and Dr. Ignacio del Río

      Version of Record online: 27 MAR 2014 | DOI: 10.1002/chem.201303653

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      Improved stability: New molybdenum and rhenium complexes are stable against ligand dissociation, and form stable supramolecular adducts with anions, employing C[BOND]H groups as the sole hydrogen bond donor groups (see figure).

    31. Yolk–Shell Structures

      Kilogram-Scale Production of SnO2 Yolk–Shell Powders by a Spray-Drying Process Using Dextrin as Carbon Source and Drying Additive (pages 5835–5839)

      Seung Ho Choi and Prof. Yun Chan Kang

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/chem.201304231

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      Not just an empty shell: Tin oxalate/dextrin composite powders were produced on a large scale by means of a commercial spray-drying process and transformed into single-shelled SnO2 yolk–shell powders by combustion in air at 600 °C (see figure). The SnO2 yolk–shell powders showed superior electrochemical properties as anode materials for lithium-ion batteries.

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