Chemistry - A European Journal

Cover image for Vol. 12 Issue 7

February 20, 2006

Volume 12, Issue 7

Pages 1831–2107

    1. Cover Picture: Dynamic Chemical Devices: Photoinduced Electron Transfer and Its Ion-Triggered Switching in Nanomechanical Butterfly-Type Bis(porphyrin)terpyridines (Chem. Eur. J. 7/2006) (page 1831)

      Myriam Linke-Schaetzel, Christopher E. Anson, Annie K. Powell, Gernot Buth, Emilio Palomares, James D. Durrant, Teodor Silviu Balaban and Jean-Marie Lehn

      Version of Record online: 10 FEB 2006 | DOI: 10.1002/chem.200690020

      Dynamic chemical devices based on a terpyridine scaffold and two appended porphyrin moieties have been synthesized. In their Full Paper on page 1931 ff., T. S. Balaban, J. D. Durrant, J.-M. Lehn et al. describe how these “butterfly-type” devices are capable of switching from an extended open geometry W to a compact closed geometry U upon cation coordination to the terpy unit. The porphyrin moieties exist in the constructs either as free bases or they can be sequentially metallated, thus giving rise to wings of different “colors”.

    2. Self-Assembled Fluorescent Chemosensors (pages 1844–1854)

      Fabrizio Mancin, Enrico Rampazzo, Paolo Tecilla and Umberto Tonellato

      Version of Record online: 30 AUG 2005 | DOI: 10.1002/chem.200500549

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      Self-organizing chemosensors: The cartoon illustrates a self-organizing chemosensor formed by the spontaneous self-organization of one receptor (gray cup) and a fluorescent reporter on a proper template. Binding of the substrate (black ball) switches off the fluorescence, allowing its detection.

    3. Ruthenium-Catalyzed Asymmetric Epoxidation of Olefins Using H2O2, Part I: Synthesis of New Chiral N,N,N-Tridentate Pybox and Pyboxazine Ligands and Their Ruthenium Complexes (pages 1855–1874)

      Man Kin Tse, Santosh Bhor, Markus Klawonn, Gopinathan Anilkumar, Haijun Jiao, Christian Döbler, Anke Spannenberg, Wolfgang Mägerlein, Herbert Hugl and Matthias Beller

      Version of Record online: 27 JAN 2006 | DOI: 10.1002/chem.200501261

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      A toolbox for catalysts: Chiral tridentate N,N,N-pyridine-2,6-bisoxazolines 3 (pybox ligands) and new N,N,N-pyridine-2,6-bisoxazines 4 (pyboxazine ligands) have been synthesized for the first time. Together with para-substituted 2,6-pyridine-dicarboxylic acids 5 (pydic), a wide range of epoxidation catalysts [Ru(pybox)(pydic)] 1 and [Ru(pyboxazine)(pydic)] 2 were synthesized and fully characterized.

    4. Ruthenium-Catalyzed Asymmetric Epoxidation of Olefins Using H2O2, Part II: Catalytic Activities and Mechanism (pages 1875–1888)

      Man Kin Tse, Santosh Bhor, Markus Klawonn, Gopinathan Anilkumar, Haijun Jiao, Anke Spannenberg, Christian Döbler, Wolfgang Mägerlein, Herbert Hugl and Matthias Beller

      Version of Record online: 24 JAN 2006 | DOI: 10.1002/chem.200501262

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      Asymmetric epoxidation of all six classes of aromatic olefins with H2O2 has been achieved in good yields with up to 84 % ee in the presence of ruthenium complexes (see scheme). This class of catalyst shows high tolerance towards functional groups under mild reaction conditions. Systematic variations of the ligands electronically and sterically provide new mechanistic insight into this reaction.

    5. Donor-Substituted 1,1,4,4-Tetracyanobutadienes (TCBDs): New Chromophores with Efficient Intramolecular Charge-Transfer Interactions by Atom-Economic Synthesis (pages 1889–1905)

      Tsuyoshi Michinobu, Corinne Boudon, Jean-Paul Gisselbrecht, Paul Seiler, Brian Frank, Nicolle N. P. Moonen, Maurice Gross and François Diederich

      Version of Record online: 3 JAN 2006 | DOI: 10.1002/chem.200501113

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      Atom economy! An extensive series of donor-substituted tetracyanobutadienes (TCBDs, two examples of which are shown here) has been prepared by short, atom-economic synthesis. Despite their twisted structures, efficient donor–acceptor π-electron conjugation in these novel chromophores was demonstrated by a variety of methods, including X-ray crystallography, UV-visible spectroscopy (depicted), and electrochemistry.

    6. Bis(calixcrown)tetrathiafulvalene Receptors (pages 1906–1914)

      María-Jesús Blesa, Bang-Tun Zhao, Magali Allain, Franck Le Derf and Marc Sallé

      Version of Record online: 18 JAN 2006 | DOI: 10.1002/chem.200500878

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      A family of electroactive receptors has been synthesized by covalent association of two calixarene platforms for spatial organization, two polyether 3D cavities for cation binding, and one electroactive tetrathiafulvalene unit to probe the complexation event (see picture). Sodium complexation changes the calixarene conformation from pinched cone to symmetrical cone, as shown by 1H NMR titration and X-ray crystallographic studies on a free receptor and a complex with two Na atoms (right). Cyclic voltammetric studies validated the electrochemical recognition concept of these assemblies.

    7. A Synthetic Camel Anti-Lysozyme Peptide Antibody (Peptibody) with Flexible Loop Structure Identified by High-Resolution Affinity Mass Spectrometry (pages 1915–1923)

      Andreas Marquardt, Serge Muyldermans and Michael Przybylski

      Version of Record online: 16 DEC 2005 | DOI: 10.1002/chem.200500785

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      Single-chain peptibody design: A fully functional anti-lysozyme peptide antibody, peptibody, was designed and synthesised from a native single-chain camel antibody, and a flexible loop structure was identified as an essential prerequisite for affinity. High-resolution affinity mass spectrometry and proteolytic paratope excision provided direct characterisation of the lysozyme–peptibody complex, and identification of the minimal paratope recognition sequence (see figure).

    8. Synthesis, Crystal Structure, and Catalytic Properties of MgCo6Ge6 (pages 1924–1930)

      Christine Gieck, Martin Schreyer, Thomas F. Fässler, Sylwia Cavet and Peter Claus

      Version of Record online: 19 DEC 2005 | DOI: 10.1002/chem.200500411

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      A remarkably high activity and selectivity in the hydrogenation of α,β-unsaturated aldehydes is attained by using the (unsupported) catalyst MgCo6Ge6 (see picture). The latter contains a combination of various chemical bond types ranging from metallic to covalent bonding.

    9. Dynamic Chemical Devices: Photoinduced Electron Transfer and Its Ion-Triggered Switching in Nanomechanical Butterfly-Type Bis(porphyrin)terpyridines (pages 1931–1940)

      Myriam Linke-Schaetzel, Christopher E. Anson, Annie K. Powell, Gernot Buth, Emilio Palomares, James D. Durrant, Teodor Silviu Balaban and Jean-Marie Lehn

      Version of Record online: 28 NOV 2005 | DOI: 10.1002/chem.200500602

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      A double-trigger-modulated optomechanical switching device with selective substrate binding for either metal atoms or tailored ligands is described. Molecular constructs were synthesised from a terpyridine scaffold and two appended porphyrin moieties and were capable of switching from an extended open geometry to a compact closed geometry upon cation coordination to the terpy unit (see scheme).

    10. Continua of Interactions between Pairs of Atoms in Molecular Crystals (pages 1941–1949)

      Paulina M. Dominiak, Anna Makal, Paul R. Mallinson, Kinga Trzcinska, Julita Eilmes, Eugeniusz Grech, Maksymilian Chruszcz, Władek Minor and Krzysztof Woźniak

      Version of Record online: 3 JAN 2006 | DOI: 10.1002/chem.200500600

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      Everything afloat! For continua of interactions including covalent/ionic bonds as well as hydrogen bonds and all other types of weak interactions for all pairs of interacting atoms, several dependencies of CP parameters on measures of separation have been obtained. A nonlinear dependence of the Laplacian on charge density has been found (see figure) and confirmed experimentally.

    11. Structural and Magnetic Properties of MnIII and CuII Tetranuclear Azido Polyoxometalate Complexes: Multifrequency High-Field EPR Spectroscopy of Cu4 Clusters with S=1 and S=2 Ground States (pages 1950–1959)

      Pierre Mialane, Carole Duboc, Jérôme Marrot, Eric Rivière, Anne Dolbecq and Francis Sécheresse

      Version of Record online: 10 JAN 2006 | DOI: 10.1002/chem.200500877

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      The first manganese–azido polyoxometalate complex is presented, as well as a tetranuclear azido polyoxometalate CuII compound that displays the strongest ferromagnetic exchange constant ever observed either in a polyoxometalate or in a diazido-bridged CuII complex (see graphic). A correlation between the bridging angle and the coupling parameter for basal–basal di-(μ-1,1-N3) CuII complexes is proposed.

    12. Selective Catalytic Oxidation of Organosulfur Compounds with tert-Butyl Hydroperoxide (pages 1960–1967)

      Antonio Chica, Giorgio Gatti, Bjorn Moden, Leonardo Marchese and Enrique Iglesia

      Version of Record online: 30 DEC 2005 | DOI: 10.1002/chem.200500858

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      Co-containing aluminophosphates: The oxidation of different sulfur compounds has been investigated by using CoAPO-5 (APO=aluminophosphate), Co/H-Y, and MoOx/Al2O3 as catalysts. CoAPO-5 (see figure) produced the highest oxidation activity and the lowest leaching of Co atoms.

    13. Interaction of Bovine Serum Albumin with Chrysotile: Spectroscopic and Morphological Studies (pages 1968–1974)

      Giuseppe Falini, Elisabetta Foresti, Isidoro G. Lesci, Bruno Lunelli, Piera Sabatino and Norberto Roveri

      Version of Record online: 16 DEC 2005 | DOI: 10.1002/chem.200500709

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      Asbestos absorbs albumin: The first morphological evidence of BSA adsorption onto synthetic chrysotile nanocrystals—an ideal reference standard with which to study the interaction of asbestos fibers with biological systems—is revealed by results of TEM and AFM analysis (TEM image shown). FTIR investigation of the adduct allowed quantification of albumin secondary-structure modifications induced by the electron-donor sites present on the nanocrystal surface.

    14. Rapid Monitoring of the Nature and Interconversion of Supported Catalyst Phases and of Their Influence upon Performance: CO Oxidation to CO2 by γ-Al2O3 Supported Rh Catalysts (pages 1975–1985)

      Mark A. Newton, Andrew J. Dent, Sofia Diaz-Moreno, Steven G. Fiddy, Bhrat Jyoti and John Evans

      Version of Record online: 10 JAN 2006 | DOI: 10.1002/chem.200500644

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      Three distinct phases of Rh nanoparticles supported upon Al2O3 were identified by using spatially and temporally resolved energy-dispersive EXAFS at the Rh K-edge during CO oxidation by O2 under plug-flow conditions. Their presence and interconversion are related to the efficiency of the catalysts in oxidising CO to CO2 (see scheme).

    15. A Spirocyclic P[BOND]S Cage Cation: Synthesis and Formation of P7S6I2+ (pages 1986–1996)

      Marcin Gonsior, Ingo Krossing and Eberhard Matern

      Version of Record online: 10 JAN 2006 | DOI: 10.1002/chem.200500142

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      Connecting main group cages? Two heptatomic main group cages may be coupled by a Ag+ ion (shown here). In this reaction P4S3I2 is ionized by Ag+ to sulfonium P4S3I+, which reacts with another P4S3I2 molecule and forms either P4S3I3+ or probably P8S6I3+. From these intermediates, the spirocyclic P7S6I2+ phosphonium ion is formed in good yields.

    16. Silver Complexes of Cyclic Hexachlorotriphosphazene (pages 1997–2008)

      Marcin Gonsior, Sasa Antonijevic and Ingo Krossing

      Version of Record online: 23 DEC 2005 | DOI: 10.1002/chem.200500236

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      Complexation or ionization? The Ag+ ion of Ag[Al(ORF)4] reacts with cyclic P3N3Cl6 by complexation to give the first structurally characterized complexes of P3N3X6 (X=halogen). Although P3N3Cl5+ formation is thermodynamically possible, the Ag+/P3N3Cl6 mixture resists ionization even at 60 °C in an ultrasonic bath (see scheme; R=C(CF3)3, R′=C(CH3)(CF3)2). The picture shows the structure of the cation in Ag(η1-P3N3Cl6)2+[Al(OR)4].

    17. An Energetic Measure of Aromaticity and Antiaromaticity Based on the Pauling–Wheland Resonance Energies (pages 2009–2020)

      Yirong Mo and Paul von Ragué Schleyer

      Version of Record online: 9 DEC 2005 | DOI: 10.1002/chem.200500376

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      Measuring stability: The Pauling–Wheland adiabatic resonance energy (the energy difference between the real conjugated system and the corresponding virtual most stable resonance structure, see scheme) has been computed based on a valence-bond-like method for various aromatic and antiaromatic systems.

    18. Molecular Design of Neutral Intramolecular Complexes Bearing Two Silicon Atoms Anchored by a Carbonyl Oxygen Atom: N,N′-Bis(silylmethyl)propylene Ureas (pages 2021–2031)

      Valery F. Sidorkin, Elena F. Belogolova and Vadim A. Pestunovich

      Version of Record online: 12 DEC 2005 | DOI: 10.1002/chem.200500498

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      An insight into the nature of the O⋅⋅⋅Si coordinate bonds in isomers 1 b and 1 c of Si,Si′-substituted N,N′-bis(silylmethyl)propylene ureas (1; X, Y=Br, Cl, F, H, OH, Me) has been achieved by using electron localization function (ELF) analysis, which revealed differences in the sizes and characters of the domains of the electron pairs of the oxygen atom in 1 ac.

    19. A Close Look at Short C[BOND]CH3⋅⋅⋅Potassium Contacts: Synthetic and Theoretical Investigations of [M2Co23-OtBu)22-OtBu)4(thf)n] (M=Na, K, Rb, thf=tetrahydrofuran) (pages 2032–2038)

      Christopher E. Anson, Wim Klopper, Jin-Shan Li, Lukasz Ponikiewski and Alexander Rothenberger

      Version of Record online: 21 DEC 2005 | DOI: 10.1002/chem.200500603

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      Close encounters of the packing kind: Close contacts of tBu groups with K atoms were observed in the solid-state structure of [K2Co23-OtBu)22-OtBu)4] (see picture), and DFT calculations on the rotational barrier of the tert-butoxy group about the axis through the C[BOND]O bond were performed. It was established that in this case the -CH3⋅⋅⋅K interactions are a consequence of the packing in the extended solid-state structure.

    20. Use of Carbonaceous Polysaccharide Microspheres as Templates for Fabricating Metal Oxide Hollow Spheres (pages 2039–2047)

      Xiaoming Sun, Junfeng Liu and Yadong Li

      Version of Record online: 23 DEC 2005 | DOI: 10.1002/chem.200500660

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      A hollow victory: A general method for synthesizing metal oxide hollow spheres has been developed by using carbonaceous polysaccharide microspheres prepared from saccharide solution as templates (see scheme). A study of the gas sensitivity of SnO2 hollow spheres revealed much reduced “recovery times”, exemplifying the distinct properties imparted by the hollow structure.

    21. The Versatility of Pentalene Coordination to Transition Metals: A Density Functional Theory Investigation (pages 2048–2065)

      Saïda Bendjaballah, Samia Kahlal, Karine Costuas, Emile Bévillon and Jean-Yves Saillard

      Version of Record online: 15 DEC 2005 | DOI: 10.1002/chem.200500765

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      Club 16 to 34: Depending on the electron count and the nature of the metal(s), η2 (predicted), η3, η5, η8, or intermediate coordination modes can be adopted by pentalene (some examples are shown here). For the mononuclear species, the most favored closed-shell electron counts are 18 and 16 metal valence electrons (MVEs), whereas for the dinuclear species, an electron count of 34 MVEs is most favored.

    22. Complex Wurtzite ZnSe Microspheres with High Hierarchy and Their Optical Properties (pages 2066–2072)

      Weitang Yao, Shu-Hong Yu, Jun Jiang and Lin Zhang

      Version of Record online: 13 JAN 2006 | DOI: 10.1002/chem.200500835

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      Architecturally controlled synthesis of ZnSe microspheres with hierarchical fractal structure in a binary solution of diethylenetriamine (DETA)–deionized water (DIW) was achieved under mild solvothermal conditions (see figure). This approach could become a new conceptual synthesis route and may provide an effective strategy to access other semiconductor materials with unusual morphologies and structures.

    23. Vibronic Coupling in Organic Semiconductors: The Case of Fused Polycyclic Benzene–Thiophene Structures (pages 2073–2080)

      Veaceslav Coropceanu, Ohyun Kwon, Brigitte Wex, Bilal R. Kaafarani, Nadine E. Gruhn, Jason C. Durivage, Douglas C. Neckers and Jean-Luc Brédas

      Version of Record online: 10 JAN 2006 | DOI: 10.1002/chem.200500879

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      Fused together: The results of photoelectron spectroscopy measurements and quantum-mechanical calculations indicate that the electronic structure of the radical-cation state of the thienobisbenzothiophene isomers is very different from that in anthradithiophene and pentacene (examples are shown here), while it closely resembles the corresponding electronic structure in pentaphene.

    24. A New Efficient Route to Chiral 1,3-Disubstituted Ferrocenes: Application to the Syntheses of (Rp)- and (Sp)-17α-[(3′-formylferrocenyl)ethynyl]estradiol (pages 2081–2086)

      Benoît Ferber, Siden Top, Richard Welter and Gérard Jaouen

      Version of Record online: 9 DEC 2005 | DOI: 10.1002/chem.200500842

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      Optically pure (Rp) and (Sp)-1-formyl-3-iodo-ferrocenes were prepared from (2S,4S)-2-ferrocenyl-4-(methoxymethyl)-1,3-dioxane. Sonogashira coupling of each of the enantiomeric iodoformylferrocenes with 17α-ethynylestradiol (EE) produced (Rp)-17α-[(3′-formylferrocenyl)ethynyl]estradiol and (Sp)-17α-[(3′-formylferrocenyl)ethynyl]estradiol, respectively (see scheme).

    25. Enhanced Solubilization of Bovine Serum Albumin in Reverse Micelles by Compressed CO2 (pages 2087–2093)

      Xiaoying Feng, Jianling Zhang, Jing Chen, Buxing Han and Dong Shen

      Version of Record online: 16 DEC 2005 | DOI: 10.1002/chem.200500812

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      Protein extraction: Compressed CO2 affects considerably the maximum solubilization of bovine serum albumin in water/AOT/isooctane reverse-micellar solutions, [BSA]max (see graph). Detailed analysis indicates that the ability of reverse micelles to extract the protein depends strongly on the stability of the reverse micelles, and a multicomplex model is proposed to explain this conclusion.

    26. Computational Study of Solvent Effects and the Vibrational Spectra of Anderson Polyoxometalates (pages 2094–2102)

      Adam J. Bridgeman

      Version of Record online: 16 DEC 2005 | DOI: 10.1002/chem.200500802

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      Contraction of the cluster and an increase of the frequencies of IR and Raman bands due to stretching of the two, cis-related molybdenum–oxygen bonds in type II Anderson heteropolyanions [TeMo6O24]6− and [IMo6O24]5− (see picture), which occur on inclusion of solvent in the cluster, were the key results of density functional calculations on these systems.

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      Preview: Chem. Eur. J. 7/2006 (page 2107)

      Version of Record online: 10 FEB 2006 | DOI: 10.1002/chem.200690022

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