Chemistry - A European Journal

Cover image for Vol. 13 Issue 31

October 26, 2007

Volume 13, Issue 31

Pages 8635–8903

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    1. Cover Picture: A New Generation of Metal String Complexes: Structure, Magnetism, Spectroscopy, Theoretical Analysis, and Single Molecular Conductance of an Unusual Mixed-Valence Linear [Ni5]8+ Complex (Chem. Eur. J. 31/2007) (page 8635)

      Isiah Po-Chun Liu, Marc Bénard, Hasan Hasanov, I-Wen Peter Chen, Wei-Hsiang Tseng, Ming-Dung Fu, Marie-Madeleine Rohmer, Chun-hsien Chen, Gene-Hsiang Lee and Shie-Ming Peng

      Article first published online: 18 OCT 2007 | DOI: 10.1002/chem.200790118

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      Mixed-Valent Compounds In their Full Paper on page 8667 ff., M. Bénard, S.-M. Peng et al. report the synthesis and discuss the magnetic and conducting properties of new pentanickel chain complexes. Reduction of the standard [Ni5]10+ core provides enhanced electron mobility and improved conductivity.

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    1. Graphical Abstract: Chem. Eur. J. 31/2007 (pages 8636–8642)

      Article first published online: 18 OCT 2007 | DOI: 10.1002/chem.200790119

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  4. Concept

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    1. Carbohydrates as Synthetic Tools in Organic Chemistry (pages 8648–8659)

      Mike M. K. Boysen

      Article first published online: 21 AUG 2007 | DOI: 10.1002/chem.200701010

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      Carbohydrates are the most abundant compounds of the chiral pool, but unlike amino acids, terpenes and alkaloids have long been shunned as starting materials for the preparation of chiral tools for asymmetric synthesis. Nevertheless over the last decades very impressive examples for chiral auxiliaries, reagents and catalysts based on carbohydrates have emerged, clearly demonstrating their usefulness in stereoselective transformations.

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    1. Porphyrin Light-Harvesting Arrays Constructed in the Recombinant Tobacco Mosaic Virus Scaffold (pages 8660–8666)

      Masayuki Endo, Mamoru Fujitsuka and Tetsuro Majima

      Article first published online: 12 SEP 2007 | DOI: 10.1002/chem.200700895

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      Light-harvesting systems: The construction of multiple porphyrin arrays in tobacco mosaic virus (TMV) assemblies by site-selective incorporation of porphyrin derivatives has been realized and the photophysical properties of such assemblies have been characterized.

    2. A New Generation of Metal String Complexes: Structure, Magnetism, Spectroscopy, Theoretical Analysis, and Single Molecular Conductance of an Unusual Mixed-Valence Linear [Ni5]8+ Complex (pages 8667–8677)

      Isiah Po-Chun Liu, Marc Bénard, Hasan Hasanov, I-Wen Peter Chen, Wei-Hsiang Tseng, Ming-Dung Fu, Marie-Madeleine Rohmer, Chun-hsien Chen, Gene-Hsiang Lee and Shie-Ming Peng

      Article first published online: 11 SEP 2007 | DOI: 10.1002/chem.200700750

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      Metal string! The first linear nickel framework in which the usual sequence of NiII atoms has been reduced by two electrons is presented. The electronic structure of the metal framework appears intermediate between a localized picture corresponding to NiII-NiI-NiII-NiI-NiII and a fully delocalized model represented as (Ni2)3+-NiII-(Ni2)3+.

    3. Non-Cytotoxic, Bifunctional EuIII and TbIII Luminescent Macrocyclic Complexes for Luminescence Resonant Energy-Transfer Experiments (pages 8678–8687)

      Anne-Claire Ferrand, Daniel Imbert, Anne-Sophie Chauvin, Caroline D. B. Vandevyver and Jean-Claude G. Bünzli

      Article first published online: 14 SEP 2007 | DOI: 10.1002/chem.200700819

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      Lighting up lanthanides: Complexes EuL3 and TbL3, with a new cyclen-based macrocyclic ligand (L3) derivatised to interact with biological materials, display efficient luminescence resonant energy transfer (LRET) to the cyanine dye Cy5 (see spectra). They are shown to be non-toxic towards several cell lines and this opens the way to their potential use in bioanalyses.

    4. Chiral Macrocyclic Aliphatic Oligoimines Derived from trans-1,2-Diaminocyclohexane (pages 8688–8695)

      Marcin Kwit, Agnieszka Plutecka, Urszula Rychlewska, Jacek Gawroński, Alexander F. Khlebnikov, Sergei I. Kozhushkov, Karsten Rauch and Armin de Meijere

      Article first published online: 27 JUL 2007 | DOI: 10.1002/chem.200700648

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      Aliphatic imines can be stable! Macrocycles (of triangular or cigar shape; see figure) obtained by cyclocondensation of enantiomerically pure trans-1,2-diaminocyclohexane and aliphatic dialdehydes of rigid structure show unusual stability and can be fully characterized spectroscopically and by X-ray diffraction analysis. When both the diamine and the dialdehyde are chiral, selective formation of the macrocycle is observed.

    5. Rational Tuning of Melting Entropies for Designing Luminescent Lanthanide-Containing Thermotropic Liquid Crystals at Room Temperature (pages 8696–8713)

      Aude Escande, Laure Guénée, Homayoun Nozary, Gérald Bernardinelli, Frédéric Gumy, Annina Aebischer, Jean-Claude G. Bünzli, Bertrand Donnio, Daniel Guillon and Claude Piguet

      Article first published online: 30 JUL 2007 | DOI: 10.1002/chem.200700560

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      The connection of a large number of divergent flexible chains in metallomesogens produces an unbalanced entropic contribution to the melting process, which is responsible for the formation of room-temperature luminescent lanthanide-containing liquid crystals (see picture).

    6. Selective Inclusion of Electron-Donating Molecules into Porphyrin Nanochannels Derived from the Self-Assembly of Saddle-Distorted, Protonated Porphyrins and Photoinduced Electron Transfer from Guest Molecules to Porphyrin Dications (pages 8714–8725)

      Takahiko Kojima, Tatsuaki Nakanishi, Ryosuke Harada, Kei Ohkubo, Seigo Yamauchi and Shunichi Fukuzumi

      Article first published online: 30 JUL 2007 | DOI: 10.1002/chem.200601654

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      Welcome! The hydrochloric acid salt of dodecaphenylporphyrin forms a 3D supramolecule with channels that are approximately one nanometer in diameter. Electron-donating guest molecules are selectively included within nanochannel (see figure). Photoinduced electron transfer occurs from the guest molecules to the porphyrin dications to form a cation radical of the guest via the excited singlet state of the porphyrin to give its cation radical, which undergoes fast disproportionation by electron hopping.

    7. Visible Light Induced Catalytic Water Reduction without an Electron Relay (pages 8726–8732)

      Leonard L. Tinker, Neal D. McDaniel, Peter N. Curtin, Courtney K. Smith, Michael J. Ireland and Stefan Bernhard

      Article first published online: 24 JUL 2007 | DOI: 10.1002/chem.200700480

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      The long-lived triplet state of a cyclometalated IrIII complex was used to reduce protons from water photo-catalytically to H2. The kinetics of the hydrogen evolution were monitored with a novel photoreactor and a maximum quantum yield of 26 % was measured for this electron relay deficient system.

    8. Monomers That Form Conducting Polymers as Structure-Directing Agents: Synthesis of Microporous Molecular Sieves Encapsulating Poly-para-phenylenevinylene (pages 8733–8738)

      Pedro Atienzar, María J. Díaz-Cabañas, Manuel Moliner, Encarna Peris, Avelino Corma and Hermenegildo García

      Article first published online: 30 JUL 2007 | DOI: 10.1002/chem.200700485

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      Silica in sieves: Monomers of poly-para-phenylenevinylene (PPV) conducting polymer were used as structure-directing agents to form microporous molecular sieves. By using conditions mimicking the silicatein α enzyme, the resulting microporous silica containing the structure-directing agent was transformed into a PPV-containing silica (see picture).

    9. Giant Polyniobate Clusters Based on [Nb7O22]9− Units Derived from a Nb6O19 Precursor (pages 8739–8748)

      Jingyang Niu, Pengtao Ma, Hongyu Niu, Jie Li, Junwei Zhao, You Song and Jingping Wang

      Article first published online: 24 JUL 2007 | DOI: 10.1002/chem.200700612

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      A giant leap: Gigantic polyniobates, such as [{H2Nb6O19}6−⊂ {[({KNb24O72H10.25}{Cu(en)2})2{Cu3(en)3(H2O)3}{Na1.5Cu1.5(H2O)8}{Cu(en)2}4]6}18−]24− (see picture), comprise a wheel-like cluster encapsulating a diprotonated Lindqvist anion [H2Nb6O19]6−. The cluster anions [H23NaO8Cu24(Nb7O22)8]16− (see picture) and [H9Cu25.5O8(Nb7O22)8]28− represent giant cube-shaped frameworks. They are all made from [Nb7O22]9− fundamental building blocks derived from the Lindqvist-type hexaniobate anion [Nb6O19]8−.

    10. Three-Component Entanglements Consisting of Three Crescent-Shaped Bidentate Ligands Coordinated to an Octahedral Metal Centre (pages 8749–8753)

      Fabien Durola, Luca Russo, Jean-Pierre Sauvage, Kari Rissanen and Oliver S. Wenger

      Article first published online: 16 JUL 2007 | DOI: 10.1002/chem.200700684

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      All in a tangle: 3,3′-Biisoquinoline ligands (biiq), which bear aromatic substituents on their 8 and 8′ positions, have been used to generate interwoven systems that consist of three crescent-shaped ligands disposed around an octahedral metal centre. X-ray crystallography clearly shows that the crescent-shaped ligands do not repel each other in the tris-chelate complexes.

    11. Controlled Synthesis, Growth Mechanism, and Properties of Monodisperse CdS Colloidal Spheres (pages 8754–8761)

      Xin-Hao Li, Ji-Xue Li, Guo-Dong Li, Da-Peng Liu and Jie-Sheng Chen

      Article first published online: 3 AUG 2007 | DOI: 10.1002/chem.200700754

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      Nanoparticles: Highly monodisperse CdS colloidal spheres with a tunable size could be obtained through a facile solvothermal method; these spheres form photonic crystal films and they can also be used as a template for the preparation of other sulfide colloidal spheres (see graphic).

    12. Total Synthesis of Myxovirescin A1 (pages 8762–8783)

      Alois Fürstner, Melanie Bonnekessel, Jarred T. Blank, Karin Radkowski, Günter Seidel, Fabrice Lacombe, Barbara Gabor and Richard Mynott

      Article first published online: 4 SEP 2007 | DOI: 10.1002/chem.200700926

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      A convergent total synthesis of the antibiotic macrolide myxovirescin A1 is described that is largely based on reagent- and catalyst-controlled transformations. This includes a highly regioselective Negishi reaction of a dibromo-alkene, a palladium-catalyzed alkyl-Suzuki coupling, an exquisitely selective ring-closing alkyne metathesis, and a ruthenium-catalyzed trans-hydrosilylation tandem.

    13. Homoleptic Rare-Earth Metal(III) Tetramethylaluminates: Structural Chemistry, Reactivity, and Performance in Isoprene Polymerization (pages 8784–8800)

      Melanie Zimmermann, Nils Åge Frøystein, Andreas Fischbach, Peter Sirsch, H. Martin Dietrich, Karl W. Törnroos, Eberhardt Herdtweck and Reiner Anwander

      Article first published online: 24 JUL 2007 | DOI: 10.1002/chem.200700534

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      Ionicity overcomes covalency: The monolanthanide complexes [Ln(AlMe4)3] reveal distinct Ln3+ size-dependent coordination modes of the tetramethylaluminate ligands in the solid state (see picture)—a highly fluxional coordination scenario that is also confirmed by dynamic 1H/13C and metal-centered 27Al/89Y NMR spectroscopy.

    14. Multifunctionalization of Dendrimers through Orthogonal Transformations (pages 8801–8810)

      Poorva Goyal, Kunsang Yoon and Marcus Weck

      Article first published online: 16 MAY 2007 | DOI: 10.1002/chem.200700129

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      Drug delivery vehicle: A methodology to synthesize polyamide-based dendrimers that have two different single orthogonal functional handles, namely, an aldehyde and an azide is demonstrated (see figure). These handles allow dual chemical ligation of dendrimers to a wide variety of biologically significant molecules in almost quantitative yields.

    15. The Change of the State of an Endohedral Fullerene by Encapsulation into SWCNT: A Raman Spectroelectrochemical Study of Dy3N@C80 Peapods (pages 8811–8817)

      Martin Kalbáč, Ladislav Kavan, Markéta Zukalová, Shangfeng Yang, Jiří Čech, Siegmar Roth and Lothar Dunsch

      Article first published online: 30 JUL 2007 | DOI: 10.1002/chem.200700089

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      Peas in a pod! Dy3N@C80@SWCNT endohedral fullerene peapods have been synthesized and characterized by Raman spectroscopy (see figure) and in-situ Raman spectroelectrochemistry.

    16. Gas-Phase Reactivity of Metavanadate [VO3] towards Methanol and Ethanol: Experiment and Theory (pages 8818–8829)

      Tom Waters, Anthony G. Wedd and Richard A. J. O'Hair

      Article first published online: 27 JUL 2007 | DOI: 10.1002/chem.200700619

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      Alcohol dehydration: The metavanadate anion [VO3] dehydrates methanol to eliminate water and form [VO22-OCH2)] (see scheme), which features an [η2-C,O-OCH2]2− ligand formed by formal removal of two protons from methanol. Theoretical calculations indicate that the reaction occurs by an intramolecular hydrogen-atom-transfer pathway through the intermediate alkoxo anion [VO2(OH)(OCH3)].

    17. C1-Symmetric Versus C2-Symmetric Ligands in Enantioselective Copper–Bis(oxazoline)-Catalyzed Cyclopropanation Reactions (pages 8830–8839)

      José M Fraile, José I. García, Anja Gissibl, José A. Mayoral, Elísabet Pires, Oliver Reiser, Marta Roldán and Isabel Villalba

      Article first published online: 2 AUG 2007 | DOI: 10.1002/chem.200700681

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      Boxes need not beC2symmetric: The use of asymmetric chiral bis(oxazoline) (Box) ligands that lack C2 symmetry can lead to high enantioselectivities in the CuI-catalyzed cyclopropanation reaction of styrene with ethyl diazoacetates (see figure). Computational mechanistic studies allow this unexpected behavior to be explained through the existence of highly disfavored reaction channels, even for reactions that use asymmetric ligands.

    18. Shape- and Phase-Controlled Synthesis of Monodisperse, Single-Crystalline Ternary Chalcogenide Colloids through a Convenient Solution Synthesis Strategy (pages 8840–8846)

      Weimin Du, Xuefeng Qian, Jie Yin and Qiang Gong

      Article first published online: 26 JUL 2007 | DOI: 10.1002/chem.200700618

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      Worlds colloid! Monodisperse, single-crystalline pyramidal CuInS2 and rectangular AgInS2 colloids were successfully synthesized through a convenient and improved solvothermal process that uses hexadecylamine as a capping reagent. This approach is simple and inexpensive and could pave a new way for the synthesis of other pure or doped functional materials.

    19. A Hydrophilic Cyclodextrin Duplex Forming Supramolecular Assemblies by Physical Cross-Linking of a Biopolymer (pages 8847–8857)

      Olivia Bistri, Karim Mazeau, Rachel Auzély-Velty and Matthieu Sollogoub

      Article first published online: 26 JUL 2007 | DOI: 10.1002/chem.200700800

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      Duplexed: A new hydrophilic cyclodextrin duplex has been synthesised and shown to physically cross-link a modified biopolymer, adamantane-grafted chitosan (see figure). This hydrophilic duplex showed very different behaviour to that of an amphiphilic duplex described previously.

    20. Strong Magnetic Interactions through Weak Bonding Interactions in Organometallic Radicals: Combined Experimental and Theoretical Study (pages 8858–8866)

      Thomas Cauchy, Eliseo Ruiz, Olivier Jeannin, Mitsushiro Nomura and Marc Fourmigué

      Article first published online: 27 JUL 2007 | DOI: 10.1002/chem.200700081

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      Strong magnetic interactions through π stacking: The presence of weak intermolecular interactions between [CpNi(dithiolate)] molecules produces strong antiferromagnetic couplings, especially in the complex [CpNi(adt)], in which a Cp⋅⋅⋅Cp contact functions as an exchange pathway. Density functional theory calculations support this and show the presence of an important delocalization of the spin density on the Cp rings (see figure).

    21. Photoreactivity and Photopolymerization of Silicon-Bridged [1]Ferrocenophanes in the Presence of Terpyridine Initiators: Unprecedented Cleavage of Both Iron–Cyclopentadienyl Bonds in the Presence of Chlorosilanes (pages 8867–8876)

      Wing Yan Chan, Alan J. Lough and Ian Manners

      Article first published online: 26 JUL 2007 | DOI: 10.1002/chem.200700420

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      Photoactivated iron–Cp bond cleavage: Photolysis of a sila[1]ferrocenophane in the presence of 4,4′,4′′-tri-tert-butyl-2,2′:6′,2′′-terpyridine and Me3SiCl results in the unprecedented cleavage of both iron–Cp bonds in the ferrocenophane (see scheme); a bis(terpyridine)iron(II) salt is formed and the silane fragment of the ferrocenophane is released. No reaction is observed in the absence of light. Under the same conditions, but in the absence of the chlorosilane, high-molecular-weight polyferrocenylsilane is formed.

    22. Indium-Mediated Selective Introduction of a 1,3-Butadien-2-yl Group at the C4-Position in 2-Azetidinones and Application of 1,3-Diene-Tethered 2-Azetidinones in the Diels–Alder Reaction (pages 8877–8883)

      Kooyeon Lee and Phil Ho Lee

      Article first published online: 17 AUG 2007 | DOI: 10.1002/chem.200700796

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      Application of a 1,3-butadien-2-ylation and Diels–Alder reaction: The reaction of 4-acetoxy-2-azetidinones with organoindium reagents selectively produced 2-azetidinones, which contain a 1,3-butadienyl-2-yl group at the C4-position in good yields. The Diels–Alder reaction of 4-[(1-methylene)prop-2-enyl]-2-azetidinones with a variety of dienophiles provided 2-azetidinones with valuable functional-group-substituted six-membered rings at the C4-position in good yields (see scheme).

    23. Productive Synthesis and Properties of Polydiaminoanthraquinone and Its Pure Self-Stabilized Nanoparticles with Widely Adjustable Electroconductivity (pages 8884–8896)

      Xin-Gui Li, Hu Li and Mei-Rong Huang

      Article first published online: 24 JUL 2007 | DOI: 10.1002/chem.200700541

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      Multifunctional nanospheres: Fine poly(1,5-diaminoanthraquinone) particles were synthesized (see scheme), and the structure, properties, and multifunctionality of the particles were systematically characterized by changing the polymerization conditions. Polymerization under certain conditions affords nanoparticles with intrinsic self-stability, inherent semiconductivity, widely adjustable conductivity, high thermostability, strong silver-ion adsorbability, and photoluminescence.

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      Preview: Chem. Eur. J. 32/2007 (page 8903)

      Article first published online: 18 OCT 2007 | DOI: 10.1002/chem.200790121

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