Chemistry - A European Journal

Cover image for Vol. 20 Issue 10

March 3, 2014

Volume 20, Issue 10

Pages 2677–2965

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. You have free access to this content
      Cover Picture: Double Carom[BOND]H Activation Associated with Etheral Oxygen Insertion to Phenazine Architecture in Oxidisable Ruthenium(III) Complexes: A Mechanistic Insight (Chem. Eur. J. 10/2014) (page 2677)

      Suman K Roy, Dr. Subhas Samanta, Dr. Nabanita Saha Chowdhury, Dr. Tapan K. Mondal and Prof. Dr. Sreebrata Goswami

      Version of Record online: 25 FEB 2014 | DOI: 10.1002/chem.201490037

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      The first examples of metal-mediated (using RuIII complexes) aromatic ring hydroxylation through ethereal oxygen insertion between two activated ortho-carbons of two different aryl rings are described by S. Goswami et al. in their Communication on page 2712 ff. Three similar reactions exemplify aromatic ring hydroxylation through double Carom[BOND]H activation. Mechanistic studies reveal the involvement of multiple metal redox states and nucleophilic addition of water at activated aromatic rings.

    2. You have free access to this content
      Inside Cover: The High-Throughput Synthesis and Phase Characterisation of Amphiphiles: A Sweet Case Study (Chem. Eur. J. 10/2014) (page 2678)

      Dr. George C. Feast, Dr. Oliver E. Hutt, Dr. Xavier Mulet, Dr. Charlotte E. Conn, Dr. Calum J. Drummond and Dr. G. Paul Savage

      Version of Record online: 25 FEB 2014 | DOI: 10.1002/chem.201490038

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      A sweet case study by C. J. Drummond, G. P. Savage et al. resulted in a library of amphiphiles with sugar head groups by using high-throughput click chemistry. Several of the amphiphiles self-assembled into complex three- dimensional structures, such as the bicontinuous gyroid cubic phase. For more details see the Full Paper on page 2783 ff.

    3. You have free access to this content
      Back Cover: C(sp2)-Coupled Nitronyl Nitroxide and Iminonitroxide Diradicals (Chem. Eur. J. 10/2014) (page 2968)

      Dr. Svyatoslav Tolstikov, Prof. Evgeny Tretyakov, Dr. Sergey Fokin, Dr. Elizaveta Suturina, Prof. Galina Romanenko, Dr. Artem Bogomyakov, Dr. Dmitri Stass, Dr. Alexander Maryasov, Prof. Matvey Fedin, Prof. Nina Gritsan and Prof. Victor Ovcharenko

      Version of Record online: 25 FEB 2014 | DOI: 10.1002/chem.201490041

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      Nitronyl and imino nitroxide diradicals,  being stable heteroatom analogues of the 1,1,2,3,3-pentamethylenepropane, have been synthesized and investigated. Despite the very close proximity of two radical moieties, the diradicals have almost degenerate singlet and triplet states (J/k=−7.4 and −6.0 K). The main reason for this is the disjoint nature of their nonbonding molecular orbitals. For more details see the Full Paper by N. Gritsan, V. Ovcharenko et al. on page 2793 ff.

  2. Cover Profile

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. You have free access to this content
      Double Carom[BOND]H Activation Associated with Etheral Oxygen Insertion to Phenazine Architecture in Oxidisable Ruthenium(III) Complexes: A Mechanistic Insight (page 2680)

      Suman K Roy, Dr. Subhas Samanta, Dr. Nabanita Saha Chowdhury, Dr. Tapan K. Mondal and Prof. Dr. Sreebrata Goswami

      Version of Record online: 25 FEB 2014 | DOI: 10.1002/chem.201400172

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      “This work originated from our recent interest in metal-promoted Carom[BOND]H activation reactions.” Read more about the story behind the cover in the Cover Profile and about the research itself on page 2712 ff. (DOI: 10.1002/chem.201303932)

  3. Graphical Abstract

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

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

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. Cross-Coupling Reactions

      Mixed-Ligand Catalysts: A Powerful Tool in Transition-Metal-Catalyzed Cross-Coupling Reactions (pages 2698–2702)

      Yuting Fan, Mei Cong and Ling Peng

      Version of Record online: 13 FEB 2014 | DOI: 10.1002/chem.201304715

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      Mix'n'match: The “mixed-ligand” concept has recently emerged; by combining and capitalizing on the superiority of each individual ligand already available, an expedient way can be achieved to reach a larger extent of catalytic diversity and efficacy (see scheme). Given the availability of a wealth of ligands, it is reasonable to have great expectations for the original application of mixed-ligand catalytic systems and their important value in organic synthesis.

  6. Communications

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

      Two Series of Sandwich Frameworks Based on Two Different Kinds of Nanosized Lanthanide(III) and Copper(I) Wheel Cluster Units (pages 2704–2711)

      Wei-Hui Fang, Dr. Jian-Wen Cheng and Prof. Dr. Guo-Yu Yang

      Version of Record online: 20 FEB 2014 | DOI: 10.1002/chem.201304165

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      Synergistic coordination: Two types of synergistic coordination between organic 4-pyridin-4-yl-benzonate and oxalate/acetate ligands, as well as organic 4-pyridin-4-yl-benzonate and inorganic Br/I ligands were simultaneously observed in two series of sandwich frameworks based on linkages of two distinct layered networks of nanosized LnIII and CuI wheels, La18/3Cu@Cu24 in FJ-21 and Ln24/Cu2@Cu24 in FJ-22, by 4-pyridin-4-yl-benzoate ligands (see figure).

    2. C[BOND]H Bond Activation

      Double Carom[BOND]H Activation Associated with Etheral Oxygen Insertion to Phenazine Architecture in Oxidisable Ruthenium(III) Complexes: A Mechanistic Insight (pages 2712–2717)

      Suman K Roy, Dr. Subhas Samanta, Dr. Nabanita Saha Chowdhury, Dr. Tapan K. Mondal and Prof. Dr. Sreebrata Goswami

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/chem.201303932

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      Unprecedented examples of double aromatic ring C[BOND]H bond activation associated with C[BOND]O bond formation reactions to phenazine architecture in RuIII complexes are presented. The chemical transformations have led to formation of new RuIV complexes with angular pentacyclo heterocyclic ligands (see scheme).

    3. Magnetic Resonance Imaging

      Diblock-Copolymer-Mediated Self-Assembly of Protein-Stabilized Iron Oxide Nanoparticle Clusters for Magnetic Resonance Imaging (pages 2718–2722)

      Sari Tähkä, Dr. Ari Laiho and Prof. Mauri A. Kostiainen

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/chem.201304070

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      Contrast boost: Superparamagnetic iron oxide nanoparticles (SPIONs) that are double-stabilized by protein (magnetoferritin) and diblock copolymer shells can be assembled into hydrodynamically stable stringlike clusters (see figure; PEO=poly(ethylene oxide), P2QVP=N-methyl-2-vinylpyridinium iodide). The longitudinal relaxivity (T1) is decreased and the transverse relaxivity (T2) is increased, thus indicating that clusters can provide considerable contrast enhancement in magnetic resonance imaging (MRI).

    4. Nanospheres

      Preparation and Unique Electrical Behaviors of Monodispersed Hybrid Nanorattles of Metal Nanocores with Hairy Electroactive Polymer Shells (pages 2723–2731)

      Tao Cai, Dr. Bin Zhang, Prof. Dr. Yu Chen, Cheng Wang, Prof. Dr. Chun Xiang Zhu, Prof. Dr. Koon-Gee Neoh and Prof. Dr. En-Tang Kang

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/chem.201303970

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      A moving core: A versatile template-assisted strategy for the preparation of monodispersed rattle-type hybrid nanospheres encapsulating a movable Au nanocore in the hollow cavity of a hairy electroactive polymer shell has been reported. The as-prepared nanorattles have been dispersed into an electrically insulating polystyrene matrix and used for the first time to fabricate nonvolatile memory devices (see figure, PTEMA: poly[2-(thiophen-3-yl)ethyl methacrylate]; P3HT: poly(3-hexylthiophene), ITO=indium tin oxide).

    5. Metal Complexes

      Pseudotetrahedral Rhodium(I) Complexes (pages 2732–2736)

      Ana M. Geer, Alejandro Julián, Dr. José A. López, Prof. Dr. Miguel A. Ciriano and Dr. Cristina Tejel

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/chem.201304569

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      Tetrahedral rhodium: The use of a four-electron π-donor, such as an alkyne, in combination with a strongly donating scorpionate ligand, in the coordination sphere of a rhodium(I) center leads to pseudotetrahedral environments. Such a geometry was unknown in rhodium(I) chemistry. The complex (see graphic; Rh, yellow; P, purple; C, grey; B, orange) promotes H[BOND]C bond activation and C[BOND]C coupling reactions under very mild conditions.

    6. Nanostructures

      One-Pot Synthesis of Pd-Loaded SnO2 Yolk–Shell Nanostructures for Ultraselective Methyl Benzene Sensors (pages 2737–2741)

      Young Jun Hong, Ji-Wook Yoon, Prof. Jong-Heun Lee and Prof. Yun Chan Kang

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/chem.201304502

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      A yolk with many shells: A continuous, single-step, and large-scale preparation of Pd-catalyst-loaded SnO2 yolk–shell spheres is demonstrated (see figure). These nanostructures show an unusually high response and selectivity to methyl benzenes, such as xylene and toluene, with very low cross-responses to various interfering gases, making them suitable for precise monitoring of indoor air quality.

    7. Rational Synthesis of Triangular Au–Ag2S Hybrid Nanoframes with Effective Photoresponses (pages 2742–2745)

      Dr. Lin Xu, Dr. Zongyou Yin, Dr. Shao-Wen Cao, Zhanxi Fan, Xiao Zhang, Prof. Hua Zhang and Prof. Can Xue

      Version of Record online: 13 FEB 2014 | DOI: 10.1002/chem.201304545

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      I was framed! Triangular Au–Ag2S hybrid nanoframes were synthesised by using Ag nanoprisms as templates through gold coating, etching and sulfuration (see figure; FTO=fluorine-doped tin oxide). These Au–Ag2S hybrid nanoframes exhibit effective photocurrent responses for potential photoelectrochemical applications.

    8. Synthetic Methods

      A Versatile and Highly Efficient Method for 1-Chlorination of Terminal and Trialkylsilyl-Protected Alkynes (pages 2746–2749)

      Dr. Nurbey Gulia, Bartłomiej Pigulski, Marta Charewicz and Dr. Sławomir Szafert

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/chem.201303680

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      A general chlorination of alkynes: A highly efficient one-pot procedure for the preparation of 1-chloroalkynes and 1-chlorobutadiynes from terminal and trialkylsilyl-protected precursors is reported (see figure; TMS=trimethylsilyl, TES=triethylsilyl, TBDMS=tert-butyldimethylsilyl, TIPS=triisopropylsilyl). This convenient reaction, proceeding under mild conditions, utilizes N-chlorosuccinimide as the chlorinating agent and tolerates a range of functional groups.

    9. Difluoromethylation

      Direct α-Siladifluoromethylation of Lithium Enolates with Ruppert-Prakash Reagent via C[BOND]F Bond Activation (pages 2750–2754)

      Ryota Hashimoto, Toshiaki Iida, Dr. Kohsuke Aikawa, Prof. Dr. Shigekazu Ito and Prof. Dr. Koichi Mikami

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/chem.201304473

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      Reaching for Ruppert–Prakash: The direct α-siladifluoromethylation of lithium enolates with the Ruppert–Prakash reagent (CF3TMS) is shown to construct tertiary and quaternary carbon centers (see scheme). The Ruppert–Prakash reagent can be employed as a siladifluoromethyl cation (TMSCF2+) equivalent by C[BOND]F bond activation due to the strong interaction between lithium and fluorine atoms.

    10. Synthetic Methods

      Synthesis of Highly Functionalized Diaryl Ethers by Copper-Mediated O-Arylation of Phenols using Trivalent Arylbismuth Reagents (pages 2755–2760)

      Cynthia Crifar, Pauline Petiot, Tabinda Ahmad and Prof. Alexandre Gagnon

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/chem.201303684

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      Highly functionalized diaryl ethers were prepared by a copper(II) acetate mediated O-arylation reaction of phenols using trivalent organobismuthanes (see scheme). The reaction is performed under simple conditions and tolerates a wide diversity of functional groups on the phenol and on the organobismuth reagent. Substoichiometric amounts of catalyst can be used by performing the reaction under an oxygen atmosphere. The N-arylation of pyridones is also reported. FG=functional group.

    11. Surface Chemistry

      Surface-Junction Effects on Interfacial Electron Transfer between Bis(terpyridine)iron(II) and Hydrogen-Terminated Silicon(111) Electrode (pages 2761–2764)

      Hiroaki Maeda, Dr. Ryota Sakamoto and Prof. Dr. Hiroshi Nishihara

      Version of Record online: 13 FEB 2014 | DOI: 10.1002/chem.201304588

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      Anchor ligands: The electron-transfer rate constant (kET) for [Fe(tpy)2] (tpy=2,2′:6′,2′′-terpyridine) complexes linked by four types of anchor ligands on hydrogen-terminated Si(111) was investigated. The anchor ligands with phenylene units exhibited greater kET values in spite of their longer distance (see scheme).

    12. Organic Chemistry

      Palladium/Copper-Catalyzed Oxidative Arylation of Terminal Alkenes with Aroyl Hydrazides (pages 2765–2769)

      Yong-Gang Zhang, Xiang-Lei Liu, Zeng-Yang He, Xi-Ming Li, Hong-Jian Kang and Prof. Dr. Shi-Kai Tian

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/chem.201304696

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      Cross-coupling: An oxidative arylation reaction of terminal alkenes with simple aroyl hydrazides has been developed in the presence of a PdCl2/CuI catalyst under aerobic conditions to give a range of structurally diverse 1,2-disubstituted alkenes in moderate to excellent yields with excellent regio- and E-selectivity (see scheme; r.s.=regioselectivity).

  7. Full Papers

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

      Peptide-Based Carbohydrate Receptors (pages 2770–2782)

      Dr. Melanie Rauschenberg, Dr. Sateesh Bandaru, Dr. Mark P. Waller and Prof. Dr. Bart Jan Ravoo

      Version of Record online: 13 FEB 2014 | DOI: 10.1002/chem.201303777

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      Peptide talk: Cyclic peptides (see figure) are potent and selective receptors for carbohydrates in aqueous solution. A detailed investigation of the noncovalent interaction of two cyclic hexapeptides with a selection of monosaccharides and disaccharides in aqueous solution is described.

    2. Carbohydrate Chemistry

      The High-Throughput Synthesis and Phase Characterisation of Amphiphiles: A Sweet Case Study (pages 2783–2792)

      Dr. George C. Feast, Dr. Oliver E. Hutt, Dr. Xavier Mulet, Dr. Charlotte E. Conn, Dr. Calum J. Drummond and Dr. G. Paul Savage

      Version of Record online: 13 FEB 2014 | DOI: 10.1002/chem.201303514

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      Click, zap, boom! A new approach to the synthesis and characterisation of sugar-based amphiphiles is reported, consisting of high-throughput “click” synthesis and thermotropic and lyotropic phase characterisation using small-angle X-ray scattering (see figure).

    3. Singlet Diradicals

      C(sp2)-Coupled Nitronyl Nitroxide and Iminonitroxide Diradicals (pages 2793–2803)

      Dr. Svyatoslav Tolstikov, Prof. Evgeny Tretyakov, Dr. Sergey Fokin, Dr. Elizaveta Suturina, Prof. Galina Romanenko, Dr. Artem Bogomyakov, Dr. Dmitri Stass, Dr. Alexander Maryasov, Prof. Matvey Fedin, Prof. Nina Gritsan and Prof. Victor Ovcharenko

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/chem.201302681

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      Playing with spins: New C(sp2)-spaced nitronyl nitroxide and iminonitroxide diradicals are reported. The exciting feature of these diradicals inherent in their nature is the very low singlet–triplet energy splitting. A small difference in the structure of Cu(hfac)2 complexes with the nitronyl nitroxide diradical gives rise to essentially different exchange interactions between the copper and nitroxide spins (see scheme; hfac = hexafluoroacetylacetonate).

    4. Bismetallocenes

      Lanthanoid–Transition-Metal Bonding in Bismetallocenes (pages 2804–2811)

      Dr. Mikhail V. Butovskii, Dr. Benjamin Oelkers, Dr. Tobias Bauer, Dr. Jacinta M. Bakker, Dr. Viktor Bezugly, Dr. Frank R. Wagner and Prof. Dr. Rhett Kempe

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/chem.201304125

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      Bonding session: The synthesis of bismetallocenes for virtually all lanthanoids is described. Differently substituted cyclopentadienyl ligands must be used to stabilize the Ln precursors and different synthetic protocols must be applied to prepare the bimetallic complexes. Rare-earth–transition-metal covalent interactions are important for the understanding the structure (see figure).

    5. Metallogels

      Supramolecular Polymers Self-Assembled from trans-Bis(pyridine) Dichloropalladium(II) and Platinum(II) Complexes (pages 2812–2818)

      Mingming Chen, Chengsha Wei, Jiaojiao Tao, Xibo Wu, Dr. Ningdong Huang, Prof. Dr. Guobin Zhang and Prof. Dr. Liangbin Li

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/chem.201304315

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      It all starts to gel: Two trans-bis(pyridine) dichloropalladium(II)- and platinum(II)-type complexes were found to self-assemble in n-hexane to form supramolecular polymers (see figure). Metallophilic interactions were found to be involved in the aggregation process.

    6. Metathesis Reactions

      Mechanistic Studies of Hoveyda–Grubbs Metathesis Catalysts Bearing S-, Br-, I-, and N-coordinating Naphthalene Ligands (pages 2819–2828)

      Krzysztof Grudzień, Karolina Żukowska, Maura Malińska, Prof. Krzysztof Woźniak and Dr. Michał Barbasiewicz

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/chem.201303826

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      Isomerization first: A family of halogen-chelated Hoveyda–Grubbs complexes displays a cis-Cl2trans-Cl2 equilibrium in solution. Relative contents of the minor trans forms go along with the activity of the metathesis catalysts, suggesting its participation in the initiation mechanism (see figure). A unique effect of the naphthalene ligands enables control of the activity over a broad range, from moderately achieve to dormant, and was manifested in 1H NMR for complexes with repulsive H⋅⋅⋅H intraligand interactions (Mes = Mesityl).

    7. DNA Recognition

      You have full text access to this OnlineOpen article
      Metal-Ion-Regulated Miniature DNA-Binding Proteins Based on GCN4 and Non-native Regulation Sites (pages 2829–2839)

      Emmanuel Oheix and Dr. Anna F. A. Peacock

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/chem.201303747

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      Metal regulation: The transoid-to-cisoid conformational transition of polypyridine ligands upon metal-ion complexation is exploited to design peptide conjugates, based on the GCN4 transcription factor, capable of stimuli-responsive DNA recognition. Careful selection of the polypyridine linker can allow for discrimination between target sites which differ in a single nucleobase pair.

    8. Heteropolyoxoniobates

      Unprecedented High-Nuclear Transition-Metal-Cluster-Substituted Heteropolyoxoniobates: Synthesis by {V8} Ring Insertion into the POM Matrix and Antitumor Activities (pages 2840–2848)

      Jian-Qiang Shen, Dr. Qiong Wu, Ying Zhang, Dr. Zhi-Ming Zhang, Prof. Yang-Guang Li, Dr. Ying Lu and Prof. En-Bo Wang

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/chem.201303995

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      High-nuclear heteropolyoxoniobates: Reactions of hexaniobate with vanadate in the presence of Zn2+, Ni2+, or Cu2+ have furnished the first high-nuclear vanadium-cluster-substituted heteropolyoxoniobates [XNb8VIV8O44]11− (X=V, P). Nickel and zinc cations have been introduced into the heteropolyoxoniobate system for the first time, which might promise a more diverse set of structures in this family. Antitumor studies have indicated that two of these compounds exhibit effective activity against SGC-7901, SC-1680, and MG-63 cells (see figure).

    9. Hydrogen Bonds

      α-Halogenoacetanilides as Hydrogen-Bonding Organocatalysts that Activate Carbonyl Bonds: Fluorine versus Chlorine and Bromine (pages 2849–2859)

      Dr. Sylvain Koeller, Dr. Coralie Thomas, Dr. Fréderic Peruch, Dr. Alain Deffieux, Dr. Stéphane Massip, Prof. Dr. Jean-Michel Léger, Dr. Jean-Pierre Desvergne, Prof. Dr. Anne Milet and Dr. Brigitte Bibal

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/chem.201303662

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      Two are better than one or three: α-Dihalogenoacetanilides have an attractive ability to form twofold H-bonds towards C[DOUBLE BOND]O groups, involving a N[BOND]H⋅⋅⋅O⋅⋅⋅H[BOND]C interaction (see figure). These nonconventional O⋅⋅⋅H[BOND]CX2 H-bonds are shown to be strong by molecular modeling and solid-state packing. As organocatalysts, α-dihalogenoacetanilides allow the activation of C[DOUBLE BOND]O bonds in lactide, enabling full conversion into its polymer, even in the presence of a tertiary amine as cocatalyst.

    10. Charge-Density Calculations

      The Dark Side of Hydrogen Bonds in the Design of Optical Materials: A Charge-Density Perspective (pages 2860–2865)

      Dr. Yulia V. Nelyubina, Dr. Lada N. Puntus and Prof. Konstantin A. Lyssenko

      Version of Record online: 2 FEB 2014 | DOI: 10.1002/chem.201300566

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      Be aware of the dark side: Investigation of the structural, electronic and optical properties of three [Ln(H2O)9(CF3SO3)3] complexes gives unambiguous experimental evidence for a charge redistribution in the first coordination sphere of the lanthanide ion as a result of hydrogen bonds between coordinated water molecules and outer-sphere anions (see figure). Rather than increasing the luminescence efficiency, these hydrogen bonds lead to additional quenching that is unfavorable for the task-specific design of optical materials.

    11. Pollutant Degradation

      Efficient Biocatalytic Degradation of Pollutants by Enzyme-Releasing Self-Propelled Motors (pages 2866–2871)

      Dr. Jahir Orozco, Diana Vilela, Dr. Gabriela Valdés-Ramírez, Yuri Fedorak, Prof. Alberto Escarpa, Prof. Rafael Vazquez-Duhalt and Prof. Joseph Wang

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/chem.201304179

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      Keep the motor running: Catalytic degradation of pollutants by enzyme-releasing motors is reported. The first example of a self-propelled tubular motor that releases an enzyme in a controlled fashion for the efficient biocatalytic degradation of chemical pollutants is described (see figure).

    12. Supported Catalysts

      Polymeric Carbon Nitride/Mesoporous Silica Composites as Catalyst Support for Au and Pt Nanoparticles (pages 2872–2878)

      Ping Xiao, Dr. Yanxi Zhao, Tao Wang, Dr. Yingying Zhan, Dr. Huihu Wang, Prof. Jinlin Li, Prof. Arne Thomas and Junjiang Zhu

      Version of Record online: 4 FEB 2014 | DOI: 10.1002/chem.201303741

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      Highly stable and dispersed Au and Pt nanoparticles (NPs) can be prepared by a facile impregnation method in which polymeric carbon nitride (CNx)/mesoporous silica composites are used as support, whereas agglomeration of NPs occurred in the absence of carbon nitride (see figure). The supported Pt NPs are promising catalysts for heterogeneous reactions such as CO oxidation.

    13. Organic Synthesis

      A Versatile and Stereocontrolled Total Synthesis of Dihydroxylated Docosatrienes Containing a Conjugated E,E,Z-Triene (pages 2879–2887)

      Dr. Gandrath Dayaker, Dr. Thierry Durand and Dr. Laurence Balas

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/chem.201304526

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      Modification is key: Two total syntheses of dihydroxylated and noncyclic metabolites of polyunsaturated fatty acids, that is, NPD1 methyl ester epimer and its n-3 docosapentaenoic acid (DPA)-derived analogue, were achieved from a highly functionalized and late advanced pivotal intermediate (see scheme).

    14. Sensors

      Aptamer-Based Luminescence Energy Transfer from Near-Infrared-to-Near-Infrared Upconverting Nanoparticles to Gold Nanorods and Its Application for the Detection of Thrombin (pages 2888–2894)

      Fei Yuan, Prof. Dr. Hongqi Chen, Juan Xu, Yiyan Zhang, Yong Wu and Prof. Lun Wang

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/chem.201304556

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      LET there be luminescence! A new luminescence energy transfer (LET) system has been designed for the detection of thrombin in the near-infrared (NIR) region by utilizing NIR-to-NIR upconversion lanthanide nanophosphors (UCNPs) as the donor and gold nanorods (Au NRs) as the acceptor (see figure). The LET system was used to monitor thrombin concentrations in aqueous buffer and human blood samples. The method was also successfully applied to thrombin detection in blood samples.

    15. Enantioselectivity

      Highly Enantioselective Extraction of Underivatized Amino Acids by the Uryl-Pendant Hydroxyphenyl-Binol Ketone (pages 2895–2900)

      Dr. Haofei Huang, Qian Chen, Misun Choi, Prof. Raju Nandhakumar, Dr. Zhishan Su, Prof. Dr. Sihyun Ham and Prof. Kwan Mook Kim

      Version of Record online: 2 FEB 2014 | DOI: 10.1002/chem.201304454

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      Extracting with ELLE: The hydroxyphenyl-binol ketone forms an imine exclusively with D-amino acids (AA) under the condition of enantioselective liquid–liquid extraction (ELLE; see scheme). Multiple hydrogen bonds greatly increase the steric hindrance of the imine of L-amino acids, whose formation was not detected in the 1H NMR spectroscopic studies.

    16. BODIPY DYEmers

      Conjugated BODIPY DYEmers by Metathesis Reactions (pages 2901–2912)

      Johannes Ahrens, Dr. Birte Haberlag, Anne Scheja, Prof. Dr. Matthias Tamm and Prof. Dr. Martin Bröring

      Version of Record online: 12 DEC 2013 | DOI: 10.1002/chem.201303468

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      Metal-promoted metathesis is a valuable tool for the efficient syntheses of conjugated di- and oligochromophoric boron dipyrrin (BODIPY) systems (see figure). The BODIPY DYEmers prepared display interesting photophysical properties and show promise in current optoelectronic research.

    17. Porphyrinoids

      Iron 10-Thiacorroles: Bioinspired Iron(III) Complexes with an Intermediate Spin (S=3/2) Ground State (pages 2913–2924)

      Dimitri Sakow, Dr. Dirk Baabe, Birte Böker, Dr. Olaf Burghaus, Dr. Markus Funk, Dr. Christian Kleeberg, Dr. Dirk Menzel, Clemens Pietzonka and Prof. Dr. Martin Bröring

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/chem.201303786

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      Stabilized i.s. the key! 10-Thiacorrole is an excellent ligand to stabilize the intermediate spin (i.s., S=3/2) state of iron(III) ions in a biomimetic coordination setting. Halogenido-, pseudo-halogenido-, and cationic solvent complexes show either a rare, unperturbed i.s. state or thermal admixture of small contributions from a high-spin state (see figure). This behavior parallels findings on certain heme peroxidases and cytochromes.

    18. Ring Expansion

      Azocinoindole Synthesis by a Gold(I)-Catalyzed Ring Expansion of 2-Propargyl-β-Tetrahydrocarboline (pages 2925–2932)

      Lei Zhang, Lina Chang, Prof. Hongwen Hu, Huaqin Wang, Prof. Dr. Zhu-Jun Yao and Prof. Dr. Shaozhong Wang

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/chem.201304524

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      Route to ring expansion: A new methodology taking advantage of gold(I)-catalyzed ring expansion has been developed to assemble tricyclic 1H-azocino[5,4-b]indoles from 2-propargyl-β-tetrahydrocarbolines (see scheme; EWG= electron-withdrawing group). A mechanism involving regioselective hydroarylation, [1,2]-alkenyl migration, and carbon–carbon bond fragmentation was proposed.

    19. Magnetic Resonance Imaging

      Comprehensive Evaluation of the Physicochemical Properties of LnIII Complexes of Aminoethyl-DO3A as pH-Responsive T1-MRI Contrast Agents (pages 2933–2944)

      Dr. Zsolt Baranyai, Dr. Gabriele A. Rolla, Dr. Roberto Negri, Attila Forgács, Prof. Giovanni B. Giovenzana and Dr. Lorenzo Tei

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/chem.201304063

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      pH Switches: N-Substituted aminoethyl-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A)-based complexes were prepared to obtain pH-sensitive T1-MRI contrast agents. A detailed evaluation of the physicochemical properties of LnIII complexes was undertaken by different techniques, highlighting the structural variations triggered by the protonation of the pendant amine and the effect of the substituents on the corresponding nitrogen atom (see figure).

    20. Metal–Organic Frameworks

      New Mechanistic Insight into Stepwise Metal-Center Exchange in a Metal–Organic Framework Based on Asymmetric Zn4 Clusters (pages 2945–2952)

      Wei Meng, Huijun Li , Zhouqing Xu , Shanshan Du, Yunxia Li, Yanyan Zhu, Dr. Yi Han , Prof. Hongwei Hou, Prof. Yaoting Fan and Prof. Mingsheng Tang

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/chem.201303434

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      Metal-exchange mechanisms of a metal–organic framework based on asymmetric Zn4 clusters were elucidated. The coordination stabilities between the metal centers and the ligands as well as the preferred coordination geometries were found to be the dominant factors in the stepwise exchange processes (see figure).

    21. Aptamers

      Rational Design of a Redox-Labeled Chiral Target for an Enantioselective Aptamer-Based Electrochemical Binding Assay (pages 2953–2959)

      Dr. Julie Moreau, Lylian Challier, Noémie Lalaoui, Dr. François Mavré, Dr. Vincent Noël, Dr. Benoît Limoges, Prof. Bernd Schöllhorn and Dr. Claire Fave

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/chem.201302979

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      Trace compounds: Redox tracers have been synthesized for enantioselective electrochemical ligand binding assays by relying on the combined use of an oligonucleotide–aptamer receptor with the detection of the redox label. A rational step-by-step optimization procedure has been developed leading to a redox-labeled L-tyrosinamide derivative (see figure) conserving the high affinity towards the aptamer.

    22. Arylation

      Direct Arylation of N-Heteroarenes with Aryldiazonium Salts by Photoredox Catalysis in Water (pages 2960–2965)

      Prof. Dr. Dong Xue, Zhi-Hui Jia, Cong-Jun Zhao, Yan-Yan Zhang, Prof. Dr. Chao Wang and Prof. Dr. Jianliang Xiao

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/chem.201304120

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      Cross-coupling reaction in water: An effective visible light promoted coupling of pyridine, substituted pyridines, xanthenes, thiazole, pyrazine, and pyridazine with aryldiazonium salts in water at room temperature has been developed (see scheme).

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