Chemistry - A European Journal

Cover image for Vol. 19 Issue 43

October 18, 2013

Volume 19, Issue 43

Pages 14325–14731

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Review
    6. Communications
    7. Full Papers
    1. You have free access to this content
      Cover Picture: Carcinogenic Organic Residual Compounds Readsorbed on Thermally Reduced Graphene Materials are Released at Low Temperature (Chem. Eur. J. 43/2013) (page 14325)

      Adriano Ambrosi, Gwendeline K. S. Wong, Prof. Richard D. Webster, Prof. Zdeněk Sofer and Prof. Martin Pumera

      Article first published online: 14 OCT 2013 | DOI: 10.1002/chem.201390169

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      Carcinogenic organic residual compounds re-adsorbed on thermally reduced graphene materials are released at low temperature. This is illustrated in the picture in which small organic carcinogenic compounds rain from graphene clouds on the hot surface of a desert (Canyonlands National Park, Utah). For more details see the Full Paper by M. Pumera et al. on page 14446 ff.

    2. You have free access to this content
      Inside Cover: Allosteric Indicator Displacement Enzyme Assay for a Cyanogenic Glycoside (Chem. Eur. J. 43/2013) (page 14326)

      Dr. D. Amilan Jose, Dipl. Chem. Martin Elstner and Prof. Dr. Alexander Schiller

      Article first published online: 14 OCT 2013 | DOI: 10.1002/chem.201390170

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      Toxic cyanogenic glycosides  can be found in bitter almonds and apricots pits. A chemical biosensor for the selective detection of amygdalin in aqueous solution is reported by A. Schiller et al. in their Full Paper on page 14451 ff. The hybrid sensor consists of the enzyme β-glucosidase and a boronic acid appended viologen together with a fluorescent reporter dye. β-Glucosidase degrades the amygdalin into hydrogen cyanide, glucose and benzaldehyde. Only the released cyanide binds at the allosteric site of the boronic acid.

    3. You have free access to this content
      Back Cover: 2,4,6-Triarylphosphinines versus 2,4,6-Triarylpyridines: An Investigation of the Differences in Reactivity between Structurally Related Aromatic Phosphorus and Nitrogen Heterocycles (Chem. Eur. J. 43/2013) (page 14736)

      Jarno J. M. Weemers, Dr. Jelena Wiecko, Dr. Evgeny A. Pidko, Manuela Weber, Dr. Martin Lutz and Prof. Dr. Christian Müller

      Article first published online: 14 OCT 2013 | DOI: 10.1002/chem.201390173

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      The differences in reactivity between structurally related 2,4,6-triarylphosphinines and 2,4,6-triarylpyridines towards IrIII and PdII have been investigated. Although phosphinines undergo facile C[BOND]H activation with [Cp*IrCl2] in the presence of NaOAc, this reaction does not proceed with the corresponding pyridine derivatives. On the other hand, pyridines can be selectively ortho-metalated with Pd(OAc)2, leading to acetate-bridged dimeric species. The reaction of phosphinines with Pd(OAc)2 led instead to the formation of unusual cofacial oxidative coupling products, which consist of a phosphorus-containing cage structure. For more details, see the Full Paper by C. Müller et al. on page 14458 ff.

  2. Graphical Abstract

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

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

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

      Recent Advances in Organocatalytic Methods for Asymmetric C[BOND]C Bond Formation (pages 14346–14396)

      Dr. Ulf Scheffler and Prof. Dr. Rainer Mahrwald

      Article first published online: 20 SEP 2013 | DOI: 10.1002/chem.201301996

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      A large number of organocatalytic processes are already well established in organic synthesis. Nevertheless, the number of publications in this field is still on the increase; new important results are produced constantly. This review gives a detailed overview of the latest developments and main streams in organocatalyzed asymmetric C[BOND]C bond formation of the last three years. It is intended to outline the most important current findings focused on especially new synthetic methodologies.

      Corrected by:

      Corrigendum: Corrigendum: Recent Advances in Organocatalytic Methods for Asymmetric C[BOND]C Bond Formation

      Vol. 19, Issue 47, 15794, Article first published online: 12 NOV 2013

  5. Communications

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

      Highly Efficient Etherification of Silanes by Using a Gold Nanoparticle Catalyst: Remarkable Effect of O2 (pages 14398–14402)

      Dr. Takato Mitsudome, Yuya Yamamoto, Akifumi Noujima, Dr. Tomoo Mizugaki, Prof. Dr. Koichiro Jitsukawa and Prof. Dr. Kiyotomi Kaneda

      Article first published online: 24 SEP 2013 | DOI: 10.1002/chem.201302807

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      O2 is acting! A nanosized hydroxylapatite-supported Au nanoparticle (NP) catalyst exhibited high activity under aerobic conditions, and various silyl ethers could be obtained from diverse combinations of silanes with alcohols. Moreover, O2 was found to act not as a stoichiometric oxidizing reagent, but as a non-consumed promoter, significantly boosting the catalytic activity of AuNPs (see figure).

    2. Organic Synthesis

      A Copper(I)-Catalyzed Three-Component Domino Process: Assembly of Complex 1,2,3-Triazolyl-5-Phosphonates from Azides, Alkynes, and H-Phosphates (pages 14403–14406)

      Prof. Dr. Lingjun Li, Guoliang Hao, Prof. Dr. Anlian Zhu, Xincui Fan, Prof. Dr. Guisheng Zhang and Prof. Dr. Lihe Zhang

      Article first published online: 23 SEP 2013 | DOI: 10.1002/chem.201303324

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      Three is better than one! A new copper-catalyzed tricomponent reaction of a terminal alkyne, organic azide, and H-phosphate (CuAA[P]C) leads to a structurally diverse polysubstituted 1,2,3-triazolyl-5-phosphonate, which provides an efficient tool for the direct introduction of phosphonic acid groups by a “click reaction” (see scheme).

    3. Organic Chemistry

      Biocatalytic Michael-Type Additions of Acetaldehyde to Nitroolefins with the Proline-Based Enzyme 4-Oxalocrotonate Tautomerase Yielding Enantioenriched γ-Nitroaldehydes (pages 14407–14410)

      Dr. Edzard M. Geertsema, Yufeng Miao, Pieter G. Tepper, Pim de Haan, Dr. Ellen Zandvoort and Prof. Dr. Gerrit J. Poelarends

      Article first published online: 24 SEP 2013 | DOI: 10.1002/chem.201302351

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      Call me Michaelase: The enzyme 4-oxalocrotonate tautomerase (4-OT) promiscuously catalyzes the Michael-type addition of acetaldehyde to a collection of aromatic and aliphatic nitroolefins with high stereoselectivity producing precursors of γ-aminobutyric acid (GABA) analogues (see scheme).

    4. Synthetic Methods

      Synthesis of Alkylbismuths by Regiodivergent Carbobismuthination of Simple Alkenes (pages 14411–14415)

      Dr. Yoshihiro Nishimoto, Midori Takeuchi, Dr. Makoto Yasuda and Prof. Dr. Akio Baba

      Article first published online: 2 OCT 2013 | DOI: 10.1002/chem.201302194

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      Switchable regioselectivity: This study represents the first carbobismuthination of alkenes achieved by the treatment of an alkene with a bismuth halide and a ketene silyl acetal. This reaction is particularly noteworthy in that a change in the type of halogen on a bismuth atom very easily switched the regioselectivity (see scheme).

    5. Indole Alkylation

      General and Selective C-3 Alkylation of Indoles with Primary Alcohols by a Reusable Pt Nanocluster Catalyst (pages 14416–14419)

      Dr. S. M. A. Hakim Siddiki, Dr. Kenichi Kon and Dr. Ken-ichi Shimizu

      Article first published online: 20 SEP 2013 | DOI: 10.1002/chem.201302464

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      The platinum rule: Heterogeneous, additive-free C-3 selective alkylation of indoles by aliphatic and aromatic alcohols proceeded under transfer hydrogenation conditions with the reusable Pt/θ-Al2O3 catalyst (see scheme; TON=turnover number).

    6. Trifluoromethylation

      Copper-Catalyzed Trifluoromethylation–Cyclization of Enynes: Highly Regioselective Construction of Trifluoromethylated Carbocycles and Heterocycles (pages 14420–14424)

      Dr. Pin Gao, Xiao-Biao Yan, Tao Tao, Fan Yang, Ting He, Xian-Rong Song, Prof. Dr. Xue-Yuan Liu and Prof. Dr. Yong-Min Liang

      Article first published online: 23 SEP 2013 | DOI: 10.1002/chem.201303025

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      Regioselective trifluoromethylation–cyclization: A method for copper-catalyzed trifluoromethylation–cyclization of simple enynes using the C[BOND]C triple bond as a nucleophile is reported for the first time (see scheme). The reaction proceeds efficiently in a highly regioselective manner to give various 5- or 6-exo-dig carbocycles and heterocycles in moderate to high yields.

    7. Catalysis

      The Aminocyclodextrin/Pd(OAc)2 Complex as an Efficient Catalyst for the Mizoroki–Heck Cross-Coupling Reaction (pages 14425–14431)

      Kuppusamy Kanagaraj and Prof. Dr. Kasi Pitchumani

      Article first published online: 23 SEP 2013 | DOI: 10.1002/chem.201301863

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      An aminocyclodextrin/Pd(OAc)2 complex is used as an efficient, reusable catalyst in the Mizoroki–Heck reaction of aryl halides/triflates with olefins to give carbon–carbon-coupled products in good to excellent yields. This simple, efficient catalytic system is applicable to a wide range of aryl and heteroaryl halides/triflates and olefins. This environmentally benign procedure is less hazardous, milder, uses a catalytic amount of ligand and Pd(OAc)2, avoids an inert atmosphere, and catalyst recovery and reusability are achieved.

    8. Palladium Catalysis

      A Highly Efficient Palladium-Catalyzed Decarboxylative ortho-Acylation of Azobenzenes with α-Oxocarboxylic Acids: Direct Access to Acylated Azo Compounds (pages 14432–14436)

      Dr. Hongji Li, Prof. Pinhua Li, Hui Tan and Prof. Dr. Lei Wang

      Article first published online: 23 SEP 2013 | DOI: 10.1002/chem.201301818

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      Avoiding additives: A highly efficient and mild Pd-catalyzed decarboxylative ortho-acylation of azobenzenes with α-oxocarboxylic acids was developed that provides an alternative route to acylated azo compounds. This decarboxylative acylation process was completed in the absence of any additives at ambient temperature, to afford the acylated azobenzenes in moderate to good yields (see scheme).

  6. Full Papers

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

      Enhanced Magneto-optical Properties of Semiconductor EuS Nanocrystals Assisted by Surface Plasmon Resonance of Gold Nanoparticles (pages 14438–14445)

      Akira Kawashima, Prof. Dr. Takayuki Nakanishi, Prof. Dr. Tamaki Shibayama, Prof. Dr. Seiichi Watanabe, Prof. Dr. Koji Fujita, Prof. Dr. Katsuhisa Tanaka, Prof. Dr. Hitoshi Koizumi, Prof. Dr. Koji Fushimi and Prof. Dr. Yasuchika Hasegawa

      Article first published online: 18 SEP 2013 | DOI: 10.1002/chem.201302259

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      Photo-information technology: A new EuS–Au nanosystem—in which EuS and Au nanocrystals are linked by organic molecules—for use in future photo-information technology is reported. The Faraday rotation angle of the EuS–Au nanosystem is dependent on the Au particle size and interparticle distance. Enhancement of the Faraday rotation of EuS–Au nanosystems was observed (see scheme).

    2. Graphene

      Carcinogenic Organic Residual Compounds Readsorbed on Thermally Reduced Graphene Materials are Released at Low Temperature (pages 14446–14450)

      Adriano Ambrosi, Gwendeline K. S. Wong, Prof. Richard D. Webster, Prof. Zdeněk Sofer and Prof. Martin Pumera

      Article first published online: 5 SEP 2013 | DOI: 10.1002/chem.201302413

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      Taking out the trash: The composition of the potentially carcinogenic organic compounds that are adsorbed onto the graphene material during the thermal reduction/exfoliation of graphite oxide has been investigated. Such compounds can be easily released during the following processing steps even at temperatures as low as 50 °C (see figure).

    3. Sensors

      Allosteric Indicator Displacement Enzyme Assay for a Cyanogenic Glycoside (pages 14451–14457)

      Dr. D. Amilan Jose, Dipl. Chem. Martin Elstner and Prof. Dr. Alexander Schiller

      Article first published online: 7 OCT 2013 | DOI: 10.1002/chem.201302801

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      Cyanide detection: A chemical biosensor for the selective detection of the cyanogenic glycoside amygdalin in aqueous solution is reported. The hybrid sensor consists of the enzyme β-glucosidase and a boronic acid appended viologen together with a fluorescent reporter dye. β-Glucosidase degrades the amygdalin into hydrogen cyanide, glucose, and benzaldehyde. Only the released cyanide binds at the allosteric site of the receptor (see scheme).

    4. Heterocycles

      2,4,6-Triarylphosphinines versus 2,4,6-Triarylpyridines: An Investigation of the Differences in Reactivity between Structurally Related Aromatic Phosphorus and Nitrogen Heterocycles (pages 14458–14469)

      Jarno J. M. Weemers, Dr. Jelena Wiecko, Dr. Evgeny A. Pidko, Manuela Weber, Dr. Martin Lutz and Prof. Dr. Christian Müller

      Article first published online: 2 OCT 2013 | DOI: 10.1002/chem.201302441

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      The right balance: Although phosphinines undergo facile C[BOND]H activation with [Cp*IrCl2]2 in the presence of NaOAc, this reaction does not proceed with the corresponding pyridine derivatives. The latter can be selectively ortho-metalated with Pd(OAc)2, leading to acetate-bridged dimeric species. The treatment of phosphinines with Pd(OAc)2 led to unusual cofacial oxidative coupling products.

    5. Indium Complexes

      Non-Innocent Ligand Effects on Low-Oxidation-State Indium Complexes (pages 14470–14483)

      Christopher J. Allan, Benjamin F. T. Cooper, Hugh J. Cowley, Jeremy M. Rawson and Charles L. B. Macdonald

      Article first published online: 13 SEP 2013 | DOI: 10.1002/chem.201301881

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      Not so In-nocent: Insights into the nature of substituent effects in “non-innocent” α-diimine ligands are obtained by using unusually stable indium(I) compounds as a probe (see scheme; Mes=mesityl, OTf=trifluoromethanesulfonate, Dipp=2,6-diisopropylphenyl). The results are derived from investigations that include synthesis, X-ray crystallography, cyclic voltammetry, EPR spectroscopy, and DFT calculations.

    6. Terpenes

      Titanocene(III)-Catalyzed 6-exo Versus 7-endo Cyclizations of Epoxypolyprenes: Efficient Control and Synthesis of Versatile Terpenic Building Blocks (pages 14484–14495)

      Dr. José Justicia, Dr. Tania Jiménez, Dr. Delia Miguel, Rafael Contreras-Montoya, Dr. Rachid Chahboun, Prof. Enrique Álvarez-Manzaneda, Daniel Collado-Sanz, Prof. Diego J. Cárdenas and Dr. Juan M. Cuerva

      Article first published online: 17 SEP 2013 | DOI: 10.1002/chem.201302575

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      Ti for terpenes: A complete study on the selectivity of the titanocene(III)-catalyzed cyclization of epoxypolyprenes is presented. The requirements for the formation of six- or seven-membered rings during these cyclizations are determined, yielding complete selectivity for the 6-exo or 7-endo cyclization process (see scheme). This procedure opens the possibility to prepare excellent building blocks for the synthesis of polycyclic compounds.

    7. Amphiphiles

      Luminescent Amphiphilic 2,6-Bis(1,2,3-triazol-4-yl)pyridine[BOND]Platinum(II) Complexes: Synthesis, Characterization, Electrochemical, Photophysical, and Langmuir–Blodgett Film-Formation Studies (pages 14496–14505)

      Dr. Yongguang Li, Dr. Le Zhao, Dr. Anthony Yiu-Yan Tam, Dr. Keith Man-Chung Wong, Prof. Dr. Lixin Wu and Prof. Dr. Vivian Wing-Wah Yam

      Article first published online: 16 SEP 2013 | DOI: 10.1002/chem.201301788

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      Platinum LB film: A series of 2,6-bis(1,2,3-triazol-4-yl)pyridine–platinum(II) complexes has been synthesized and characterized. Their electrochemical and photophysical properties have also been studied. Two amphiphilic platinum(II) complexes were found to form stable and reproducible Langmuir–Blodgett (LB) films at the air/water interface. These LB films have been characterized in detail (see figure).

    8. Donor–Acceptor Systems

      Assembling a Phthalocyanine and Perylenediimide Donor–Acceptor Hybrid through a Platinum(II) Diacetylide Linker (pages 14506–14514)

      Dr. Ángel J. Jiménez, Michael Sekita, Dr. Esmeralda Caballero, Dr. M. Luisa Marcos, Dr. M. Salomé Rodríguez-Morgade, Prof. Dr. Dirk M. Guldi and Prof. Tomás Torres

      Article first published online: 13 SEP 2013 | DOI: 10.1002/chem.201301630

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      Linked up: The photophysical behavior of a phthalocyanine (Pc)–perylenediimide (PDI) Pc-Pt-PDI donor–acceptor hybrid (see figure), in which a platinum diacetylide linker disrupts electronic communication between the two electroactive components, is compared with that of the corresponding conjugated Pc-PDI array in terms of photoinduced generation of a long-lived charge-separation state.

    9. Alkaloids

      Spontaneous Formation of Nitrarine and Polycyclic Skeletons Related to Nitraria Indolic Alkaloids under Non-Enzymic Conditions (pages 14515–14520)

      Dr. Edmond Gravel, Abha Harfouche, Dr. Rim Salame, Karine Leblanc, Dr. Alexandre Maciuk and Prof. Dr. Erwan Poupon

      Article first published online: 12 SEP 2013 | DOI: 10.1002/chem.201301877

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      Just mix! The simple mixing of tryptamine and C5 units (presumably derived from L-lysine in nature) allowed the spontaneous formation of several indolic skeletons, including the unique structure of nitrarine (see scheme).

    10. Magnetic Properties

      Chemical Inhomogeneity, Short-Range Order, and Magnetism in the LiNiO2-NiO Solid Solution (pages 14521–14531)

      Phillip T. Barton, Dr. Y. Daniel Premchand, Dr. Philip A. Chater, Prof. Ram Seshadri and Prof. Matthew J. Rosseinsky

      Article first published online: 13 SEP 2013 | DOI: 10.1002/chem.201301451

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      Track and field: A comprehensive structural and magnetic study of the important layered magnetic solid solution between LiNiO2 and NiO reveals the importance of coherent internal interfaces in what appears, crystallographically, to be a single-phase material. These internal interfaces give rise to some of the unusual magnetic behavior, including exchange-biased hysteresis loops (see figure).

    11. Organocatalysis

      Organocatalyzed Aldol Reaction between Pyridine-2-carbaldehydes and α-Ketoacids: A Straightforward Route towards Indolizidines and Isotetronic Acids (pages 14532–14539)

      Dr. Virginie Liautard, Damien Jardel, Clotilde Davies, Muriel Berlande, Dr. Thierry Buffeteau, Dr. Dominique Cavagnat, Dr. Frédéric Robert, Dr. Jean-Marc Vincent and Prof. Dr. Yannick Landais

      Article first published online: 13 SEP 2013 | DOI: 10.1002/chem.201302264

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      BIPpity boppity boo: Asymmetric aldol reactions between pyridine carbaldehydes and α-ketoacids were shown to provide isotetronic acids or their corresponding pyridinium salts with high enantioselectivities by using benzimidazole pyrrolidine (BIP) as a catalyst. Hydrogenation of the resulting pyridinium salts led to new indolizidines with high enantioselectivity and diasterocontrol (see scheme).

    12. Gold Chemistry

      Gold(I) and Gold(III) Trifluoromethyl Derivatives (pages 14540–14552)

      Dr. Sonia Martínez-Salvador, Prof. Dr. Larry R. Falvello, Dr. Antonio Martín and Dr. Babil Menjón

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201302142

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      Race for gold! The depicted highly sensitive carbonyl compound, the acetonitrile solvate, and the well-behaved thioether derivative (tht=tetrahydrothiophene; see scheme) are ranked, in that order, as convenient synthons of the “Au(CF3)” fragment.

    13. Density Functional Calculations

      DFT Study on the Recovery of Hoveyda–Grubbs-Type Catalyst Precursors in Enyne and Diene Ring-Closing Metathesis (pages 14553–14565)

      Dr. Francisco Núñez-Zarur, Dr. Xavier Solans-Monfort, Prof. Roser Pleixats, Dr. Luis Rodríguez-Santiago and Prof. Mariona Sodupe

      Article first published online: 20 SEP 2013 | DOI: 10.1002/chem.201301898

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      Origin of the recovered catalyst: DFT calculations on models of ring-closing diene and enyne metathesis reactions show that, although the regeneration of second-generation Hoveyda–Grubbs precursors is favorable (see figure), other reactions that involve the active carbenes present lower energy barriers. Thus, the amount of recovered catalyst is more likely due to incomplete precatalyst activation.

    14. Cyanides

      Effect of Cyanide Ligands on the Electronic Structure of [FeFe] Hydrogenase Active-Site Model Complexes with an Azadithiolate Cofactor (pages 14566–14572)

      Dr. Özlen F. Erdem, Dr. Matthias Stein, Dr. Sandeep Kaur-Ghumaan, Dr. Edward J. Reijerse, Dr. Sascha Ott and Prof. Dr. Wolfgang Lubitz

      Article first published online: 13 SEP 2013 | DOI: 10.1002/chem.201302467

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      Tuning the bridge: A close synthetic model of the [2 Fe]H subcluster in the [FeFe] hydrogenase active site is presented. Calculations reveal that the CN/PMe3 ligand coordinated to the iron core is electronically coupled to the amine in the azadithiolate (adt) bridge (see figure). The better σ-donating properties of the CN ligand in comparison to PMe3 enable more spin density to be transferred to the adt unit.

    15. Semiconductors

      Thiepin-Fused Heteroacenes: Simple Synthesis, Unusual Structure, and Semiconductors with Less Anisotropic Behavior (pages 14573–14580)

      Zhengxu Cai, Hantang Zhang, Dr. Hua Geng, Dr. Zitong Liu, Sifen Yang, Hewei Luo, Dr. Lang Jiang, Dr. Qian Peng, Dr. Guanxin Zhang, Dr. Jianming Chen, Prof. Yuanping Yi, Prof. Wenping Hu and Prof. Deqing Zhang

      Article first published online: 17 SEP 2013 | DOI: 10.1002/chem.201302114

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      Thiepin-fused OFETs: The first planar thiepin-fused heteroacenes were synthesized by using a simple one-pot reaction. Organic field-effect transistors (OFETs) with microcrystals were fabricated and theoretical calculations were carried out to understand the semiconducting behaviors (see figure). The results reveal that thiepin-containing conjugated systems are interesting for application in future organic electronic devices.

    16. Molecular Recognition

      Conformational Selection in Glycomimetics: Human Galectin-1 Only Recognizes syn-Ψ-Type Conformations of β-1,3-Linked Lactose and Its C-Glycosyl Derivative (pages 14581–14590)

      Dr. Paloma Vidal, Dr. Virginia Roldós, Dr. María del Carmen Fernández-Alonso, Dr. Boris Vauzeilles, Prof. Dr. Yves Bleriot, Prof. Dr. F. Javier Cañada, Dr. Sabine André, Prof. Dr. Hans-Joachim Gabius, Prof. Dr. Jesús Jiménez-Barbero, Dr. Juan Félix Espinosa and Dr. Sonsoles Martín-Santamaría

      Article first published online: 17 SEP 2013 | DOI: 10.1002/chem.201301244

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      Trapping one conformer: Combination of transferred (TR)-NOESY experiments, which include the bioactive conformation determination with molecular modeling, have enabled the explanation, in structural chemistry terms, of a conformational selection process in the recognition of C-glycomimetics by a human galectin (see figure).

    17. Metal–Organic Frameworks

      Controllable Syntheses of Porous Metal–Organic Frameworks: Encapsulation of LnIII Cations for Tunable Luminescence and Small Drug Molecules for Efficient Delivery (pages 14591–14599)

      Dr. Yun Wang, Dr. Jin Yang, Dr. Ying-Ying Liu and Prof. Dr. Jian-Fang Ma

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201300144

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      Flexibile ligands: The flexible hexacarboxylate ligand 1,2,3,4,5,6-hexakis(3-carboxyphenyloxymethylene)benzene (H6L) was used to synthesize the porous metal–organic frameworks [Zn3(L)(H2O)2]3 DMF7 H2O (MOF-1) and [(CH3)2NH2]6[Ni3(L)2(H2O)6]3 DMF15 H2O (MOF-2) under solvothermal conditions. MOF-1 can encapsulate Ln3+ ions for tunable luminescence (see figure) and small drug molecules for efficient delivery.

    18. Noncovalent Interactions

      σ-Hole Bond Versus Hydrogen Bond: From Tetravalent to Pentavalent N, P, and As Atoms (pages 14600–14611)

      Prof. Dr. Sławomir J. Grabowski

      Article first published online: 3 SEP 2013 | DOI: 10.1002/chem.201302030

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      σ-Hole in one? The molecular graph and the contour map of the electron density of NFH3+⋅⋅⋅NCH complex in the plane containing the N⋅⋅⋅N σ-hole bond is presented (see figure).

    19. Hydrogen Bonds

      Ion-Pairing of Phosphonium Salts in Solution: C[BOND]H⋅⋅⋅Halogen and C[BOND]H⋅⋅⋅π Hydrogen Bonds (pages 14612–14630)

      Dr. Johannes Ammer, Dr. Christoph Nolte, Prof. Dr. Konstantin Karaghiosoff, Sebastian Thallmair, Dr. Peter Mayer, Prof. Dr. Regina de Vivie-Riedle and Prof. Dr. Herbert Mayr

      Article first published online: 6 SEP 2013 | DOI: 10.1002/chem.201204561

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      Hydrogen bonds: The 1H NMR chemical shifts of the C(α)[BOND]H protons of benzhydryl and benzyl triphenylphosphonium salts in CD2Cl2 solution strongly depend on the counter-anions (see graphic). The large downfield shifts result from C[BOND]H⋅⋅⋅X hydrogen bonds with the anions X, which is confirmed by quantum chemical calculations and by the crystal structures. The BPh4 anion forms C[BOND]H⋅⋅⋅Ph hydrogen bonds causing upfield shifts of the benzyl protons. IR spectra show red- or blue-shifts depending on X.

    20. Host–Guest Systems

      Improved Stereochemical Analysis of Conformationally Flexible Diamines by Binding to a Bisporphyrin Molecular Clip (pages 14631–14638)

      Sara Norrehed, Dr. Henrik Johansson, Prof. Dr. Helena Grennberg and Prof. Dr. Adolf Gogoll

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201300533

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      Clipped ensembles: Conformational restriction within a bisporphyrin molecular clip allowed the determination of relative stereochemistry in acyclic molecules with several stereogenic centers (see figure). Bound, in contrast to free, molecules were accessible for an NMR spectroscopic analysis of molecular flexibility in solution (NAMFIS) on the basis of intramolecular NOEs.

    21. Chemosensors

      Multimodal Use of New Coumarin-Based Fluorescent Chemosensors: Towards Highly Selective Optical Sensors for Hg2+ Probing (pages 14639–14653)

      Dr. Carla Bazzicalupi, Dr. Claudia Caltagirone, Dr. Zenfeng Cao, Dr. Qibin Chen, Prof. Corrado Di Natale, Dr. Alessandra Garau, Prof. Dr. Vito Lippolis, Dr. Larisa Lvova, Dr. Honglai Liu, Prof. Dr. Ingemar Lundström, Dr. M. Cristina Mostallino, Mattia Nieddu, Prof. Roberto Paolesse, Prof. Dr. Luca Prodi, Massimo Sgarzi and Dr. Nelsi Zaccheroni

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201302090

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      Catcher in the tap: The optical response to metal ions of new coumarin-based fluorescent chemosensors was studied in different media from solution, to cells in vitro, in the presence of silica core/polyethylene glycol (PEG) shell nanoparticles or in polyvinyl chloride (PVC)-based polymeric membranes. The doped membranes were used to develop an optical sensing array for Hg2+ ions probing in real matrices based on the computer screen photo-assisted technique (CSPT) (see figure).

    22. Supramolecular Self-Assembly

      Synthesis, Properties, and Remarkable 2 D Self-Assembly at the Liquid/Solid Interface of a Series of Triskele-Shaped 5,11,17-Triazatrinaphthylenes (TrisK) (pages 14654–14664)

      Dr. Hélène Bertrand , Dr. Régis Guillot, Dr. Marie-Paule Teulade-Fichou and Dr. Denis Fichou

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201300705

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      Seeing molecular orbitals “on the bench”: STM at the liquid/solid interface has revealed the remarkable 2D self-assembling properties of the TrisK compounds. In particular, it has shown that TrisK-H-OC12 forms three concomitant self-organised 2D phases based on row-packing arrangements (see microscope images). This 2D polymorphism arises from slow ordering due to the presence of three long dodecyloxy chains on the molecular backbone. Individual molecules can be imaged by STM with spectacular intramolecular resolution.

    23. Nanogenerators

      Length-Dependent Charge Generation from Vertical Arrays of High-Aspect-Ratio ZnO Nanowires (pages 14665–14674)

      Vivian Farías Rivera, Florian Auras, Paolo Motto, Dr. Stefano Stassi, Dr. Giancarlo Canavese, Dr. Edvige Celasco, Prof. Thomas Bein, Prof. Barbara Onida and Dr. Valentina Cauda

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201204429

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      Good zinc-ing: 1D ZnO nanostructures were obtained by hydrothermal growth on seeded conductive substrates. Nanowire density, length, and aspect-ratio studies reveal different piezoelectric properties as a function of length. The longer the nanowire, the lower the carrier concentration and the higher the charge generated when applying mechanical compressive stress (see figure).

    24. Imaging Agents

      Multifunctional Nanoprobe for MRI/Optical Dual-Modality Imaging and Radical Scavenging (pages 14675–14681)

      Dr. Mingming Zhen, Dr. Junpeng Zheng, Dr. Yifan Wang, Prof. Chunying Shu, Prof. Fabao Gao, Prof. Jing Zou, Prof. Ilmari Pyykkö and Prof. Chunru Wang

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201301601

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      A fluorescent fullerene nanoplatform was designed to cluster Gd-DTPA, a small-molecule contrast agent for magnetic resonance imaging. Thus, a multifunctional agent with MRI/optical dual-modality imaging and radical-scavenging properties was obtained (see figure). The combination of enhanced MRI/optical performance and local treatment of lesions may potentiate the medical paradigm of “detect and treat/prevent” in combating human diseases related to reactive oxygen species.

    25. Isomerization

      Conversion of trans-Diboran(4)yl Platinum Complexes into Their cis-Bisboryl Analogues (pages 14682–14686)

      Prof. Dr. Holger Braunschweig, Dr. Alexander Damme and Dr. Thomas Kupfer

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201301827

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      trans-forming: Diboran(4)yl complex trans-[(iPr3P)2Pt(Br){B(NMe2)B(NMe2)Br}] is readily converted into its cis-bisboryl analogue by treatment with chelating bisphosphines (see scheme). The forced cis configuration of the phosphine ligands thus induces a change in the preferred reaction site of the diborane(4) with respect to oxidative addition.

    26. C[BOND]C Coupling

      A Convenient Alumination of Functionalized Aromatics by Using the Frustrated Lewis Pair Et3Al and TMPMgCl⋅LiCl (pages 14687–14696)

      Dipl.-Chem. Andreas Unsinn, Dr. Stefan H. Wunderlich, Dr. Anukul Jana, Prof. Dr. Konstantin Karaghiosoff and Prof. Dr. Paul Knochel

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201301869

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      The power of frustration: A wide range of polyfunctional aryltriethylaluminate reagents were prepared at a convenient temperature range (−5 to 25 °C) by in situ preparation of the frustrated Lewis pair Et3Al–TMPMgCl⋅LiCl (TMP=2,2,6,6-tetramethylpiperidyl). The protocol tolerates a wide range of functional groups and an efficient alumination proceeds without a large excess of base (see scheme).

    27. Homogeneous Catalysis

      Electronic Tuning of Iron–Oxo-Mediated C[BOND]H Activation: Effect of Electron-Donating Ligand on Selectivity (pages 14697–14701)

      Yutaka Hitomi, Kengo Arakawa and Masahito Kodera

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201302111

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      Selective C[BOND]H activation: A series of iron(III) monamido complexes has been prepared and examined with respect to their catalytic activity for C[BOND]H hydroxylation with H2O2. As the substituent group becomes more electron withdrawing, both the selectivity and the turnover number increase, although the selectivity of epoxidation shows the opposite trend (see figure).

    28. Metal Complexes

      Acetylene Dithiolate Linking up the [Tp′W(CO)(CN)] Moiety with RuII or PdII (pages 14702–14711)

      Prof. Dr. Wolfram W. Seidel, Woldemar Dachtler, Julia Semmler, Marco Tänzler, Manuel Folk and Dr. Alexander Villinger

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201301192

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      Trapping the elusive beast: Dinuclear complexes with acetylene dithiolate bridging units are accessible using a one-pot transformation involving 2-(trimethylsilyl)ethyl substituted acetylene dithiol, an appropriate metal precursor, and a fluoride source (see scheme; Tp′=hydrotris(3,5-dimethylpyrazolyl)borate). These dithiolene type complexes show an extensive delocalisation of states over the acdt2– bridge.

    29. Energy Storage

      Towards Highly Stable Storage of Sodium Ions: A Porous Na3V2(PO4)3/C Cathode Material for Sodium-Ion Batteries (pages 14712–14718)

      Wei Shen, Cong Wang, Prof. Dr. Haimei Liu and Prof. Wensheng Yang

      Article first published online: 6 SEP 2013 | DOI: 10.1002/chem.201300005

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      Storage facility: A uniform carbon-coated porous Na3V2(PO4)3 cathode material of sodium-ion batteries has been fabricated and demonstrates an excellent rate property and cycling stability for sodium storage (see figure).

    30. Nucleic Acids

      Effects of Six-Membered Carbohydrate Rings on Structure, Stability, and Kinetics of G-Quadruplexes (pages 14719–14725)

      Dr. Jun Zhou, Dr. Michael Abramov, Dr. Fengwu Liu, Dr. Samir Amrane, Dr. Anne Bourdoncle, Prof. Piet Herdewijn and Dr. Jean-Louis Mergny

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201301743

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      Sweets for G-quadruplexes: G-quadruplexes substituted with different six-membered carbohydrate rings (see scheme; HNA: hexitol nucleic acid; CeNA: cyclohexenyl nucleic acid; ANA: altritol nucleic acid; B: base) exhibit conformational, thermal, and kinetic properties that depend on the structure and location of the modification.

    31. Group 14 Elements

      Zwitterionic Base-Stabilized Digermadistannacyclobutadiene and Tetragermacyclobutadiene (pages 14726–14731)

      Hui-Xian Yeong, Dr. Hong-Wei Xi, Dr. Yongxin Li, Dr. Sophy Bhasi Kunnappilly, Prof. Dr. Bozhen Chen, Prof. Dr. Kai-Chung Lau, Prof. Dr. Hajime Hirao, Prof. Dr. Kok Hwa Lim and Prof. Dr. Cheuk-Wai So

      Article first published online: 11 SEP 2013 | DOI: 10.1002/chem.201300447

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      Heavy elements: Zwitterionic base-stabilized digermadistannacyclobutadiene (1) and tetragermacyclobutadiene (2) were synthesized by simple procedures (see scheme). X-ray structural data and theoretical studies show that these compounds have a planar and rhombic charge-separated structure. They are also nonaromatic.

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