Chemistry - A European Journal

Cover image for Vol. 18 Issue 38

September 17, 2012

Volume 18, Issue 38

Pages 11841–12151

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Communications
    6. Full Papers
    1. You have free access to this content
      Cover Picture: Intrinsic Electric Fields in Ionic Liquids Determined by Vibrational Stark Effect Spectroscopy and Molecular Dynamics Simulation (Chem. Eur. J. 38/2012) (page 11841)

      Shiguo Zhang, Rui Shi, Xiangyuan Ma, Liujin Lu, Yude He, Xiaohu Zhang, Prof. Yanting Wang and Prof. Youquan Deng

      Version of Record online: 10 SEP 2012 | DOI: 10.1002/chem.201290163

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      The real reasons for the outstanding features in/of ionic liquids remain poorly understood and are ascribed to the so-called “ionic liquid effect/environment”. In the Communication by Y. Deng et al on page 11904 ff., they identify and quantify the intrinsic electric field by vibrational Stark effect spectroscopy and molecular dynamics simulations. Both theoretical and experimental results demonstrate that the intrinsic electric fields are slightly higher than but still comparable to those in common molecular solvents, which are surprisingly weaker than expected.

    2. You have free access to this content
      Inside Cover: Vapochromic Ionic Liquids from Metal–Chelate Complexes Exhibiting Reversible Changes in Color, Thermal, and Magnetic Properties (Chem. Eur. J. 38/2012) (page 11842)

      Yusuke Funasako, Prof. Dr. Tomoyuki Mochida, Prof. Dr. Kazuyuki Takahashi, Dr. Toshihiro Sakurai and Dr. Hitoshi Ohta

      Version of Record online: 10 SEP 2012 | DOI: 10.1002/chem.201290164

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      Multifunctional liquids that exhibit reversible responses to vapors and gases have been developed. These are ionic liquids containing cationic metal–chelate complexes of CuII and NiII, exhibiting vapochromism, thermochromism, diamagnetic–paramagnetic changes, and liquid–solid phase transformations depending on the coordination strength of the vapor molecules to the metal center of the cation, see the Full Paper by T. Mochida et al. on page 11929 ff.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Communications
    6. Full Papers
  3. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Communications
    6. Full Papers
  4. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Communications
    6. Full Papers
    1. Nanostructures

      Optimizing TiO2 Nanotube Top Geometry for Use in Dye-Sensitized Solar Cells (pages 11862–11866)

      Nooshin Mir, Kiyoung Lee, Indhumati Paramasivam and Prof. Dr. Patrik Schmuki

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/chem.201202002

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      Recombination dynamics: For TiO2 nanotube-based dye-sensitized solar cells, the efficiency can be drastically enhanced by a synergetic effect that occurs when using nanowire-ended nanotubes in combination with an adequate nanoparticle decoration (see figure).

    2. Cage Compounds

      Formation of Ti28Ln Cages, the Highest Nuclearity Polyoxotitanates (Ln=La, Ce) (pages 11867–11870)

      Yaokang Lv, Janina Willkomm, Dr. Michal Leskes, Dr. Alexander Steiner, Timothy C. King, Prof. Lihua Gan, Dr. Erwin Reisner, Dr. Paul T. Wood and Prof. Dominic S. Wright

      Version of Record online: 21 AUG 2012 | DOI: 10.1002/chem.201201827

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      The solvothermal reactions of Ti(OEt)4 with LnCl3 (Ln=La, Ce) produced new Ti28Ln cages, in which the Ln3+ ions are coordinated within a metallocrown arrangement, which represents the highest nuclearity cages of this type (see figure).

    3. Cross-Coupling

      Flash Generation of a Highly Reactive Pd Catalyst for Suzuki–Miyaura Coupling by Using a Flow Microreactor (pages 11871–11875)

      Dr. Aiichiro Nagaki, Naofumi Takabayashi, Yuya Moriwaki and Prof. Jun-ichi Yoshida

      Version of Record online: 17 AUG 2012 | DOI: 10.1002/chem.201201579

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      Superflash! Flash chemistry enables the use of highly reactive unstable species as catalysts for chemical synthesis. Fast micromixing of a solution of [Pd(OAc)2] and that of tBu3P in 1:1 mole ratio gave a solution of a highly reactive unstable species, which was immediately transferred to a vessel by using a flow microreactor, in which Suzuki–Miyaura coupling was conducted (see scheme).

    4. Metal-Organic Frameworks

      Zeolitic Boron Imidazolate Frameworks with 4-Connected Octahedral Metal Centers (pages 11876–11879)

      Dr. Fei Wang, Yu-Bo Shu, Prof. Dr. Xianhui Bu and Prof. Dr. Jian Zhang

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/chem.201202377

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      Solvent selection! The organically templated co-assembly between tetrahedral [B(imidazolate)4] and [Co(ac)]+ units leads to two previously unknown zeolitic boron imidazolate frameworks with ACO and ABW topologies (denoted BIF-22 and BIF-23; e-urea=ethyleneurea), respectively. BIF-22 is chiral and shows interesting CO2 selectivity over N2 and CH4.

    5. Asymmetric Catalysis

      Asymmetric Allylic Alkylation of Acyclic Allylic Ethers with Organolithium Reagents (pages 11880–11883)

      Dr. Manuel Pérez, Dr. Martín Fañanás-Mastral, Dr. Valentín Hornillos, Dr. Alena Rudolph, Dr. Pieter H. Bos, Dr. Syuzanna R. Harutyunyan and Prof. Dr. Ben L. Feringa

      Version of Record online: 21 AUG 2012 | DOI: 10.1002/chem.201202251

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      A highly efficient, regio- and enantioselective CuI/phosphoramidite-catalyzed asymmetric allylic alkylation of allyl ethers with organolithium reagents is reported (see scheme). The use of organolithium reagents is essential for this catalytic C[BOND]C bond formation due to their compatibility with different Lewis acids. The versatility of allylic ethers under the copper-catalyzed reaction conditions with organolithium reagents is demonstrated in the shortest synthesis of (S)-Arundic acid.

    6. Cross-Coupling Reactions

      Palladium-Catalyzed Cross-Coupling Reactions of Electron-Deficient Alkenes with N-Tosylhydrazones: Functional-Group-Controlled C[BOND]C Bond Construction (pages 11884–11888)

      Prof. Dr. Huanfeng Jiang, Wei Fu and Huoji Chen

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/chem.201202051

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      In the zone: A palladium-catalyzed cross-coupling reaction of electron-deficient alkenes with N-tosylhydrazones, which affords diverse C[BOND]C bonds resulting from the functional-group-controlled effect, is reported (see scheme). These cascade transformations present remarkable stereoselectivity and a high synthetic potential. The presence of water substantially promotes both reaction routes.

    7. Homologation

      New Methylene Homologation Method for Cyclic Ketones (pages 11889–11893)

      Huaqing Liu, Chunrui Sun, Nam-Kyu Lee, Dr. Roger F. Henry and Prof. Dr. Daesung Lee

      Version of Record online: 14 AUG 2012 | DOI: 10.1002/chem.201201346

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      Teaching new tricks to an old dog: By intercepting adducts between ketones and lithium trimethylsilyldiazomethane, a new Tiffeneau–Demjanov type methylene homologation could be realized in a single-step operation. Among proton sources and Lewis acids, silica gel was found to be the most effective reagent for the protonation of intermediates and their subsequent ring expansion (see scheme).

    8. Domino Reactions

      One-Pot Consecutive Reactions Based on the Synthesis of Conjugated Enones by the Re-Catalysed Meyer–Schuster Rearrangement (pages 11894–11898)

      Elio Mattia, Dr. Alessio Porta, Dr. Valentina Merlini, Dr. Giuseppe Zanoni and Prof. Giovanni Vidari

      Version of Record online: 14 AUG 2012 | DOI: 10.1002/chem.201201639

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      Re catalysis in one-pot reactions: An atom-economical, one-pot strategy that involves alkyne deprotonation and a subsequent rhenium(V)-catalysed Meyer–Schuster rearrangement of the alkynol to provide α,ß-unsaturated enones in high yield has been developed (see scheme). Subsequent in situ hydride reduction or Diels–Alder reaction of the enones provided products in good-to-high overall yields.

    9. Asymmetric Synthesis

      Regioselectivity-Reversed Asymmetric Aldol Reaction of 1,3-Dicarbonyl Compounds (pages 11899–11903)

      Hongxin Liu, Prof. Huayue Wu, Zhenli Luo, Jie Shen, Guowei Kang, Bidai Liu, Zhifu Wan and Prof. Jun Jiang

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/chem.201201874

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      Reverse regioselectivity: The first catalytic asymmetric C-1 functionalization of 1,3-dicarbonyl compounds by an aldol reaction is described, which regioselectively affords 6-hydroxyhexane-2,4-dione derivatives as the only product with high optical purity of up to 93 % ee. Furthermore, this method provides a facile access to enantioenriched oxygen-containing spirooxindoles and spirobutyrolactones from simple commercial available starting materials (see scheme).

    10. Ionic Liquids

      Intrinsic Electric Fields in Ionic Liquids Determined by Vibrational Stark Effect Spectroscopy and Molecular Dynamics Simulation (pages 11904–11908)

      Shiguo Zhang, Rui Shi, Xiangyuan Ma, Liujin Lu, Yude He, Xiaohu Zhang, Prof. Yanting Wang and Prof. Youquan Deng

      Version of Record online: 21 AUG 2012 | DOI: 10.1002/chem.201201257

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      The electric fields of ionic liquids are only slightly higher than those of common molecular solvents, and are strongly structure-dependent; they noticeably decrease with anion size because of increased separation of ions, and slightly decrease as the alkyl chain elongates due to increasing spatial heterogeneity. These were the key results of vibrational Stark effect spectroscopy and molecular dynamics simulations.

    11. Polyoxometalates

      A New “Fully Reduced” Polyoxovanadate Constructed from Nanosized Triangle-Shaped [VIII3VIV18P6O60(DACH)3]}9− Cluster Anions Exhibiting Ferrimagnetic Interactions (pages 11909–11912)

      Cong-Ling Wang, Zhi-bin Zhang, Jie Fu, Prof. Yan Xu and Dun-ru Zhu

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/chem.201200261

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      Magnetic personality: A pentavalent vanadium source was employed to prepare the largest highly reduced polyoxovanadate cluster by virtue of the reducing power of 1,2-diaminocyclohexane under hydrothermal conditions. The new non-classical triangle-shaped cluster shows good catalytic selectivity for the oxidation of styrene and exhibits ferrimagnetic interactions that could make it a promising magnetic material.

    12. Organocatalysis

      Selective Access to Both Diastereoisomers in an Enantioselective Intramolecular Michael Reaction by Using a Single Chiral Organocatalyst and Application in the Formal Total Synthesis of (−)-Epibatidine (pages 11913–11918)

      Kim L. Jensen, Dr. Christian F. Weise, Dr. Gustav Dickmeiss, Fabio Morana, Dr. Rebecca L. Davis and Prof. Dr. Karl Anker Jørgensen

      Version of Record online: 21 AUG 2012 | DOI: 10.1002/chem.201202353

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      Two in one: Both diastereoisomers of 4-nitro-3-substituted cyclohexanones are accessed selectively by an intramolecular Michael reaction using a single chiral aminocatalyst (see scheme). Mechanistic studies show that the reaction is selective for the cis-diastereoisomer and that the trans-diastereoisomer arises over time. DFT calculations suggest that the cis-selectivity is due to a favorable electrostatic interaction between the iminium ion and the nucleophile.

  5. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Communications
    6. Full Papers
    1. Catalyst Inhibition

      Investigations into the Formation and Stability of Cationic Rhodium Diphosphane η6-Arene Complexes (pages 11920–11928)

      Dr. Christian Fischer, Dr. Richard Thede, Dr. Hans-Joachim Drexler, Anja König, Dr. Wolfgang Baumann and Prof. Dr. Detlef Heller

      Version of Record online: 22 AUG 2012 | DOI: 10.1002/chem.201201587

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      Hit the highway: Asymmetric hydrogenation in the presence of arenes can lead to deactivation effects in catalysis (see figure). In this paper, we report the synthesis, characterization, and determination of 20 stability constants for cationic Rh diphosphane η6-arene complexes that cause the observed inhibition effect.

    2. Ionic Liquids

      Vapochromic Ionic Liquids from Metal–Chelate Complexes Exhibiting Reversible Changes in Color, Thermal, and Magnetic Properties (pages 11929–11936)

      Yusuke Funasako, Prof. Dr. Tomoyuki Mochida, Prof. Dr. Kazuyuki Takahashi, Dr. Toshihiro Sakurai and Dr. Hitoshi Ohta

      Version of Record online: 22 AUG 2012 | DOI: 10.1002/chem.201201778

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      Vapochromism: Vapor- and gas-responsive metal-containing ionic liquids have been developed. These liquids exhibit vapochromism, thermochromism, liquid–solid phase transformation, and diamagnetic–paramagnetic changes in response to vapors (see figure).

    3. Charge Transfer

      Charge-Transfer Interactions in Tris-Donor–Tris-Acceptor Hexaarylbenzene Redox Chromophores (pages 11937–11948)

      Markus Steeger and Prof. Christoph Lambert

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/chem.201104020

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      If it ain't broke: Although superficially symmetric, a hexaarylbenzene system (see figure) that contains several amine and boron redox centers shows optical spectroscopic properties that only marginally differ from those of its asymmetric analogue, owing to the breaking of the symmetry in the excited state. In contrast, the properties of the materials, such as solubility or phase-transitions, are strongly influenced by the presence/absence of symmetry.

    4. Water Splitting

      Highly Dispersed TiO6 Units in a Layered Double Hydroxide for Water Splitting (pages 11949–11958)

      Yufei Zhao, Pengyun Chen, Dr. Bingsen Zhang, Prof. Dang Sheng Su, Shitong Zhang, Lei Tian, Prof. Jun Lu, Dr. Zhuoxin Li, Prof. Xingzhong Cao, Prof. Baoyi Wang, Prof. Min Wei, Prof. David G. Evans and Prof. Xue Duan

      Version of Record online: 27 AUG 2012 | DOI: 10.1002/chem.201201065

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      Breaking the waves: A family of photocatalysts for splitting water into hydrogen was prepared by distributing TiO6 units in an MTi-layered double hydroxide matrix (M=Ni, Zn, Mg; see figure) that displays largely enhanced photocatalytic activity with an H2-production rate of 31.4 μmol h−1 as well as excellent recyclable performance.

    5. IR Spectroscopy

      Discovering the Active Sites for C3 Separation in MIL-100(Fe) by Using Operando IR Spectroscopy (pages 11959–11967)

      Dr. Stefan Wuttke, Dr. Philippe Bazin, Dr. Alexandre Vimont, Dr. Christian Serre, Dr. You-Kyong Seo, Dr. Young Kyu Hwang, Dr. Jong-San Chang, Prof. Gérard Férey and Prof. Marco Daturi

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/chem.201201006

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      Modus operandi: A reducible Fe-based metal–organic framework (MOF) was investigated for the separation mechanism of a hydrocarbon mixture by using an operando methodology (see figure). Monitoring the material surface under gas flow, the nature and the role of the active sites were identified: the unsaturated FeII entities were highlighted as being mainly responsible for the separation effect of the propane/propene mixture.

    6. Photoacid Generators

      Development of 1-Hydroxy-2(1H)-quinolone-Based Photoacid Generators and Photoresponsive Polymer Surfaces (pages 11968–11975)

      Mohammed Ikbal, Rakesh Banerjee, Sanghamitra Atta, Avijit Jana, Dibakar Dhara, Anakuthil Anoop and Dr. N. D. Pradeep Singh

      Version of Record online: 7 AUG 2012 | DOI: 10.1002/chem.201104065

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      Facile N[BOND]O cleavage of carboxylate and sulfonate esters of 1-hydroxy-2(1H)-quinolone by UV light (λ≥310 nm) has been exploited for use as nonionic photoacid generators (PAGs) for efficient generation of carboxylic and sulfonic acids, respectively. Furthermore, photoresponsive copolymers were constructed from a styryl-substituted PAG monomer and acrylate co-monomers, and their light-controlled surface wettability was demonstrated (see figure).

    7. Domino Reactions

      Development of Domino Processes by Using 7-Silylcycloheptatrienes and Its Analogues (pages 11976–11986)

      Dr. Redouane Beniazza, Dr. Valérie Desvergnes, Dr. Emeline Girard, Dr. Brice Kauffmann, Dr. Muriel Berlande and Prof. Dr. Yannick Landais

      Version of Record online: 27 AUG 2012 | DOI: 10.1002/chem.201201527

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      Follow the path: 7-Silylmethylcycloheptatriene reacts either under thermal conditions or under Lewis acid catalysis through its norcaradiene valence isomer with various dienophiles, including acylnitroso reagents and activated aldehydes and ketones, to provide useful functionalized cyclohexa-1,3-dienes with high levels of stereocontrol (see scheme).

    8. Supramolecular Chemistry

      Herringbone and Helical Self-Assembly of π-Conjugated Molecules in the Solid State through CH/π Hydrogen Bonds (pages 11987–11993)

      Mahima Goel and Dr. Manickam Jayakannan

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/chem.201200705

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      Multiple CH/π interactions drive self-organization of custom-designed oligophenylenevinylenes with a distyrylbenzene core as the π acceptor, bulky tricyclodecanemethylene groups as CH donors, and alkyl tails as self-assembly directors. Both herringbone and helical supramolecular structures could be obtained in the solid state simply by varying the number of carbon atoms in the tails (see figure).

    9. Boranes

      Large-Scale and Facile Preparation of Pure Ammonia Borane through Displacement Reactions (pages 11994–11999)

      Dr. Xuenian Chen, Xiaoguang Bao, Beau Billet, Prof. Sheldon G. Shore and Prof. Ji-Cheng Zhao

      Version of Record online: 7 AUG 2012 | DOI: 10.1002/chem.201201342

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      Totally borane: The synthesis of pure ammonia borane (AB) by displacement reactions has been unsuccessful because of formation of the ionic byproduct, diammoniate diborane (DADB). Characterization of the DADB formation mechanism lead to the development of a large-scale synthesis of pure AB. This procedure can also be used to synthesize other amine borane complexes which had the same problem of forming ionic byproducts during displacement reactions.

      Corrected by:

      Corrigendum: Corrigendum: Large-Scale and Facile Preparation of Pure Ammonia Borane through Displacement Reactions

      Vol. 18, Issue 44, 13914, Version of Record online: 22 OCT 2012

    10. Zintl Clusters

      The Neat Ternary Solid K5−xCo1−xSn9 with Endohedral [Co@Sn9]5− Cluster Units: A Precursor for Soluble Intermetalloid [Co2@Sn17]5− Clusters (pages 12000–12007)

      Dr. Viktor Hlukhyy, Haiyan He, Laura-Alice Jantke and Prof. Dr. Thomas F. Fässler

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/chem.201201786

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      Cluster's first stand: A new type of saltlike intermetallic compound obtained by the solid-state reaction of a preformed Co[BOND]Sn alloy with K and Sn contains endohedral [Co@Sn9]5− clusters. K5−xCo1−xSn9 readily and incongruently dissolves in ethylenediamine and in the presence of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (2.2.2-crypt) to form the crystalline [K([2.2.2]crypt)]5[Co2Sn17], which contains the polyanion [Co2Sn17]5− (see figure).

    11. Conducting Materials

      Synthesis, Characterisation and Electrical Properties of Supramolecular DNA-Templated Polymer Nanowires of 2,5-(Bis-2-thienyl)-pyrrole (pages 12008–12019)

      Dr. Scott M. D. Watson, Joseph H. Hedley, Dr. Miguel A. Galindo, Dr. Said A. F. Al-Said, Prof. Nick G. Wright, Prof. Bernard A. Connolly, Dr. Benjamin R. Horrocks and Prof. Andrew Houlton

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/chem.201201495

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      Captivated and electric: Duplex DNA molecules act as effective templates for the formation of nanowires of the conducting polymer, poly-[2,5-(bis-2-thienyl)-pyrrole] (see scheme). The resulting supramolecular polymer strands are typically 7–8 nm in diameter and are shown to be electrically conducting by a variety of techniques including variable-temperature conductivity measurements on a fabricated two-terminal device.

    12. Homogeneous Catalysis

      Copper(II) Triflate Catalyzed Amination of 1,3-Dicarbonyl Compounds (pages 12020–12027)

      Thi My Uyen Ton, Fanny Himawan, Dr. Joyce Wei Wei Chang and Prof. Dr. Philip Wai Hong Chan

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/chem.201201219

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      Iminoiodanes aminate: A method to prepare α,α-acyl amino acid derivatives efficiently by Cu(OTf)2+1,10-phenanthroline-catalyzed amination of 1,3-dicarbonyl compounds with PhI[DOUBLE BOND]NSO2Ar is described (see scheme). The utility of the method was exemplified by the enantioselective synthesis of a precursor of 3-styryl-2-benzoyl-L-alanine.

    13. CO2 Sequestration

      Carbonic Anhydrase Immobilized on Encapsulated Magnetic Nanoparticles for CO2 Sequestration (pages 12028–12034)

      Dr. Mari Vinoba, Dr. Margandan Bhagiyalakshmi, Dr. Soon Kwan Jeong, Dr. Sung Chan Nam and Dr. Yeoil Yoon

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/chem.201201112

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      Thinking green: Bovine carbonic anhydrase (BCA) was covalently immobilized onto OAPS (octa(aminophenyl)silsesquioxane)-functionalized Fe3O4/SiO2 nanoparticles (Fe[BOND]CA). The enzymatic activities of the free BCA and Fe[BOND]CA were investigated by hydrolyzing p-nitrophenylacetate, and by hydration and sequestration of CO2 to CaCO3 (see figure).

    14. Fullerenes

      Selective Functionalization of Fullerenes with N,N-Dihalosulfonamides as an N1 Unit: Versatile Syntheses of Aza[60]fulleroids and Aziridino[60]fullerenes and their Application to Photovoltaic Cells (pages 12035–12045)

      Toshiki Nagamachi, Dr. Youhei Takeda, Kazuhisa Nakayama and Prof. Dr. Satoshi Minakata

      Version of Record online: 14 AUG 2012 | DOI: 10.1002/chem.201201680

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      Full steam ahead: Highly selective and versatile syntheses of aza[60]fulleroids and aziridino[60]fullerenes from C60, which utilize N,N-dihalosulfonamides as an N1 source, were developed. Photophysical, electrochemical, and thermal properties of the iminofullerenes were measured, and photovoltaic cells based on these compounds were fabricated. The power conversion efficiencies (PCEs) of the devices show moderate values ranging from 1.33 to 2.35 % (see scheme).

    15. Metal Borophosphates

      Further Examples of the P-O-P Connection in Borophosphates: Synthesis and Characterization of Li2Cs2B2P4O15, LiK2BP2O8, and Li3M2BP4O14 (M=K, Rb) (pages 12046–12051)

      Ying Wang, Prof. Dr. Shilie Pan and Yunjing Shi

      Version of Record online: 7 AUG 2012 | DOI: 10.1002/chem.201201356

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      The same, but different: Four metal borophosphates display similarly unusual anionic partial structures, and the differences among them are mainly caused by the different fundamental building unit (FBU; see figure). There are three different types of FBU; two of them offer further examples of borophosphate frameworks with a P-O-P connection.

    16. Nucleophilic Reagents

      Use of Melem as a Nucleophilic Reagent to Form the Triphthalimide C6N7(phthal)3—New Targets and Prospects (pages 12052–12058)

      Dr. Anke Schwarzer, Priv.-Doz. Dr. Uwe Böhme and Prof. Dr. Edwin Kroke

      Version of Record online: 7 AUG 2012 | DOI: 10.1002/chem.201200723

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      Nucleophilic tri-s-triazine: Melem reacts as a nucleophile with phthaloyl dichloride to form the title triphthalimide C6N7(phthal)3. Comprehensive analysis and ab initio calculations have provided useful insights into its molecular structure and properties: it is stable in air up to 500 °C and shows strong photoluminescence (see figure).

    17. Carbohydrates

      Carbohydrate–Lipid Interactions: Affinities of Methylmannose Polysaccharides for Lipids in Aqueous Solution (pages 12059–12067)

      Dr. Lan Liu, Yu Bai, Nian Sun, Li Xia, Prof. Todd L. Lowary and Prof. John S. Klassen

      Version of Record online: 14 AUG 2012 | DOI: 10.1002/chem.201201222

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      Mixing sugar and oil: The interactions between 3-O-methyl-mannose polysaccharides, extracted from Mycobacterium smegmatis or obtained by chemical synthesis, with fatty acids and a commercial mixture of naphthenic acids (see scheme) were quantified by electrospray ionization mass spectrometry.

    18. Catalytic Hydroarylation

      Ruthenium-Catalyzed Hydroarylation of Methylenecyclopropanes through C[BOND]H Bond Cleavage: Scope and Mechanism (pages 12068–12077)

      Prof. Dr. Lutz Ackermann, Dr. Sergei I. Kozhushkov and Dr. Dmitry S. Yufit

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/chem.201200406

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      A highly chemo- and site-selective ruthenium catalyst has achieved intermolecular hydroarylation reactions of methylenecyclopropanes (see scheme) through chelation assistance. The C[BOND]H bond functionalization of 2-phenylpyridine and other arenes with directing groups has been studied. Furthermore, a plausible mechanistic rationale and a catalytic cycle for these unusual ruthenium-catalyzed hydroarylation reactions are proposed.

    19. Zeolites

      “Extracting” the Key Fragment in ETS-10 Crystallization and Its Application in AM-6 Assembly (pages 12078–12084)

      Meiling Guo, Prof. Dr. Zhaochi Feng, Dr. Guanna Li, Dr. Jan P. Hofmann, Dr. Evgeny A. Pidko, Dr. Pieter C. M. M. Magusin, Qiang Guo, Prof. Dr. Bert M. Weckhuysen, Prof. Dr. Emiel J. M. Hensen, Dr. Fengtao Fan and Prof. Dr. Can Li

      Version of Record online: 10 AUG 2012 | DOI: 10.1002/chem.201200875

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      The ring's the thing: The crystallization of ETS-10 is characterized in detail. The formation of a three-membered ring species is shown to be the key step in the hydrothermal synthesis of ETS-10. These insights led to a new synthesis method for the microporous vanadosilicate AM-6 that involves intermediates which contain three-membered ring species as the initiator (see figure).

    20. Solar Cells

      High-Performance Dipolar Organic Dyes with an Electron-Deficient Diphenylquinoxaline Moiety in the π-Conjugation Framework for Dye-Sensitized Solar Cells (pages 12085–12095)

      Dr. Sie-Rong Li, Chuan-Pei Lee, Dr. Hui-Tung Kuo, Prof. Kuo-Chuan Ho and Dr. Shih-Sheng Sun

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/chem.201201000

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      Donor–acceptor systems: Six organic dyes comprised of a triphenylamine group as an electron donor, a cyanoacrylic acid as an electron acceptor, and an electron-deficient diphenylquinoxaline moiety integrated into the π-conjugated spacer between the electron donor and acceptor were synthesized (see figure). Dye-sensitized solar cells (DSSCs) based on one of the dyes produced an overall cell performance of 7.35 %, which translates to about 79 % of the intrinsic efficiency of the DSSC based on standard N719.

    21. Natural Product Analogues

      Total Synthesis of Indole-Derived Allocolchicine Analogues Exhibiting Strong Apoptosis-Inducing Activity (pages 12096–12102)

      Nikolay Sitnikov, Dr. Janna Velder, Liliane Abodo, Nicole Cuvelier, Dr. Jörg Neudörfl, Dr. Aram Prokop, Dr. Günter Krause, Prof. Dr. Aleksey Y. Fedorov and Prof. Dr. Hans-Günther Schmalz

      Version of Record online: 27 AUG 2012 | DOI: 10.1002/chem.201200083

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      Induced suicide of tumor cells: Analogues of the natural product allocolchicine containing an N-methylindole substructure (see scheme) were synthesized and found to exhibit pronounced cytotoxic and apoptosis-inducing activity against different tumor cell lines at low nanomolar or even sub-nanomolar concentrations.

    22. Photocatalysis

      Visible-Light-Induced Photocatalytic Hydrogen Production over Binuclear RuII–Bipyridyl Dye-Sensitized TiO2 without Noble Metal Loading (pages 12103–12111)

      Xiaohu Zhang, Uahengo Veikko, Jin Mao, Dr. Ping Cai and Prof. Tianyou Peng

      Version of Record online: 16 AUG 2012 | DOI: 10.1002/chem.201200725

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      Loosely attached dye [Ru2(bpy)4(BL)](ClO4)2 (bpy=2,2′-bipyridine) shows higher photosensitization and photostability for photocatalytic H2 production than tightly bound dyes with terminal carboxyl groups such as [Ru2(dcbpy)4(BL)](ClO4)2 and N719 in dye-sensitized TiO2 systems (see figure). This can be rationalized by their different coordination circumstances, physicochemical properties, and electron-injection and backward-transfer properties. (C.B.=conduction band; V.B.=valence band.)

    23. Catalyst Design

      N-Heterocyclic Carbenes and Imidazole-2-thiones as Ligands for the Gold(I)-Catalysed Hydroamination of Phenylacetylene (pages 12112–12121)

      Edwin Alvarado, Anna C. Badaj, Timothy G. Larocque and Prof. Dr. Gino G. Lavoie

      Version of Record online: 7 AUG 2012 | DOI: 10.1002/chem.201201448

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      Spilling the (car)benes: Gold(I) complexes of imidazol-2-ylidene and imidazole-2-thione were prepared and structurally characterised (see scheme). All complexes were tested for the ability to catalyse the hydroamination of phenylacetylene with substituted anilines, exclusively generating the Markovnikov product in varying yields for all anilines tested.

    24. Heterogeneous Catalysis

      Efficient Tandem Synthesis of Methyl Esters and Imines by Using Versatile Hydrotalcite-Supported Gold Nanoparticles (pages 12122–12129)

      Dr. Peng Liu, Prof. Dr. Can Li and Prof. Dr. Emiel J. M. Hensen

      Version of Record online: 14 AUG 2012 | DOI: 10.1002/chem.201202077

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      Golden support! The Mg/Al atomic ratio of hydrotalcite strongly affects the catalytic performance of supported gold nanoparticles for aerobic alcohol oxidation, one-pot oxidative esterification of alcohols to methyl esters, and tandem oxidative coupling of alcohols and amines to imines (see figure). The tunability of the base properties makes hydrotalcites ideal supports for optimal gold catalysts for green tandem synthesis under mild and base-additive-free conditions.

    25. Energy Transfer in Lanthanoids

      Dependence of the Lifetime upon the Excitation Energy and Intramolecular Energy Transfer Rates: The 5D0 EuIII Emission Case (pages 12130–12139)

      Rute A. S. Ferreira, Mariela Nolasco, Ana C. Roma, Ricardo L. Longo, Oscar L. Malta and Luis D. Carlos

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/chem.201201736

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      Lifetime control: In a wide class of EuIII-based materials the presence of an intermediate energy level that mediates the energy transfer mechanisms strongly affects the lifetime of the 5D0 state at near-resonance (see figure). The 5D0 lifetime dependence on the excitation wavelength is presented for ionic salts, polyoxometalates, nanocrystals, coordination polymers, β-diketonate complexes, organic–inorganic hybrids, foams, mesoporous silica, and layered double hydroxides.

    26. Polymer Solar Cells

      Synthesis and Photovoltaic Properties of Two-Dimensional Low-Bandgap Copolymers Based on New Benzothiadiazole Derivatives with Different Conjugated Arylvinylene Side Chains (pages 12140–12151)

      Prof. Qiang Peng, Dr. Siew-Lay Lim, Ivy Hoi-Ka Wong, M. Sc. Jun Xu and Dr. Zhi-Kuan Chen

      Version of Record online: 14 AUG 2012 | DOI: 10.1002/chem.201200730

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      2D Photovoltaic copolymers: New benzothiadiazole acceptors with different conjugated arylvinylene side chains have been designed and used to build 2D-like low-bandgap copolymers (see figure). It was found that their optical and electrochemical properties can be easily modified by changing the structures of the conjugated arylvinylene side chains. The photovoltaic properties imply that all the prepared copolymers are promising candidates for roll-to-roll manufacturing of efficient polymer solar cells.

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