Chemistry - A European Journal

Cover image for Vol. 17 Issue 33

August 8, 2011

Volume 17, Issue 33

Pages 8997–9243

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
    1. Cover Picture: Theoretical Simulations Elucidate the Role of Naphthalenic Species during Methanol Conversion within H-SAPO-34 (Chem. Eur. J. 33/2011) (page 8997)

      Dr. Karen Hemelsoet, Arno Nollet, Prof. Dr. Veronique Van Speybroeck and Prof. Dr. Michel Waroquier

      Version of Record online: 2 AUG 2011 | DOI: 10.1002/chem.201190164

      Thumbnail image of graphical abstract

      The growth process and activity of naphthalenic species during methanol conversion within the industrially important catalyst H-SAPO-34 is described using ab initio simulations on a large finite cluster model. The cover shows that addition of methyl groups is feasible, leading to larger hydrocarbon pool compounds. An actual side-chain methylation turns out to be a very slow step, and the involved species should be regarded as deactivated coke precursors challenging the steric limitations of the catalytic pore. For more details see the Full Paper by K. Hemelsoet, V. Van Speybroeck et al. on page 9083 ff.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
    1. Inside Cover: Allosteric Molecular Beacons for Sensitive Detection of Nucleic Acids, Proteins, and Small Molecules in Complex Biological Samples (Chem. Eur. J. 33/2011) (page 8998)

      Yanling Song, Liang Cui, Jie Wu, Weiting Zhang, Dr. Wei Yun Zhang, Dr. Huaizhi Kang and Prof. Chaoyong James Yang

      Version of Record online: 2 AUG 2011 | DOI: 10.1002/chem.201190165

      Thumbnail image of graphical abstract

      The working principle of a new type of probe—an allosteric molecular beacon (orange ribbon)—is depicted. The probe can bind to streptavidin (sphere with colored dots) only when it is activated by its target (green ribbon). When streptavidin microbeads are used, target-bound probes will gather on the surface of microbeads and can be easily separated from free probes and other interference species for sensitive target detection in complex biological samples. For more details see the Communication by Chaoyong Yang et al. on page 9042 ff.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
  4. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
  5. Concept

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
    1. Noncovalent Materials

      Noncovalent Water-Based Materials: Robust yet Adaptive (pages 9016–9026)

      Elisha Krieg and Dr. Boris Rybtchinski

      Version of Record online: 1 JUL 2011 | DOI: 10.1002/chem.201100809

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      Better than covalent? Noncovalent materials formed by reversible self-assembly are more adaptive than covalent ones. This adaptivity facilitates easy processing, recycling, self-healing, and stimuli-responsiveness. While noncovalent interactions are generally considered weak, strong hydrophobic interactions in water can be exploited to create noncovalent materials that are unusually stable, thus allowing practical use in real-life applications.

  6. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
    1. Aromaticity

      Möbius Aromatic [28]Hexaphyrin Phosphonium Adducts (pages 9028–9031)

      Mitsunori Inoue, Tomoki Yoneda, Dr. Katsuyuki Youfu, Dr. Naoki Aratani and Prof. Dr. Atsuhiro Osuka

      Version of Record online: 8 JUL 2011 | DOI: 10.1002/chem.201100757

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      In a twist: [28]Hexaphyrin phosphonium adducts formed from the reaction with phosphines have been identified as Möbius aromatic species. On the other hand, the Hückel aromatic [26]hexaphyrin PdII complex underwent regioselective nucleophilic reactions with phosphines to provide Möbius aromatic [28]hexaphyrin phosphonium adducts. The phosphonium ylide contribution is more dominant and hence more aromatic in the latter phosphonium PdII complexes.

    2. Asymmetric Catalysis

      Asymmetric Trienamine Catalysis for the Construction of Structurally Rigid Cyclic α,α-Disubstituted Amino Acid Derivatives (pages 9032–9036)

      Hao Jiang, Dr. Björn Gschwend, Dr. Łukasz Albrecht, Dr. Signe Grann Hansen and Prof. Karl Anker Jørgensen

      Version of Record online: 8 JUL 2011 | DOI: 10.1002/chem.201101539

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      2,4-Dienals are shown to undergo highly stereoselective Diels–Alder reactions with olefinic azlactones by asymmetric trienamine catalysis. The obtained cycloadducts are easily transformed into the corresponding cyclic α,α-disubstituted N-protected amino acid methyl esters under mild reaction conditions. Furthermore, it is demonstrated that in situ ligation of the crude cycloaddition products with amino acid hydrochloride salts leads to the formation of non-natural dipeptide motifs in a one-pot fashion.

    3. Direct Enantioselective Amination of α-Ketoesters Catalyzed by an Axially Chiral Guanidine Base (pages 9037–9041)

      Prof. Dr. Masahiro Terada, Kei Amagai, Kenichi Ando, Dr. Eunsang Kwon and Dr. Hitoshi Ube

      Version of Record online: 12 JUL 2011 | DOI: 10.1002/chem.201101076

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      β-functional! Direct enantioselective amination of α-ketoesters with azodicarboxylates was demonstrated using an axially chiral guanidine base catalyst, which enabled efficient access to enantioenriched multifunctionalized ketoesters with an aliphatic substituent at the β-position. Subsequent nucleophilic addition to the β-hydrazinyl-α-ketoester at the reactive ketone yields the corresponding β-hydrazinyl-α-hydroxy esters in high syn diastereo- and enantioselectivities (see scheme).

      Corrected by:

      Corrigendum: Corrigendum: Direct Enantioselective Amination of α-Ketoesters Catalyzed by an Axially Chiral Guanidine Base

      Vol. 17, Issue 36, 9858, Version of Record online: 22 AUG 2011

    4. Allosteric Probes

      Allosteric Molecular Beacons for Sensitive Detection of Nucleic Acids, Proteins, and Small Molecules in Complex Biological Samples (pages 9042–9046)

      Yanling Song, Liang Cui, Jie Wu, Weiting Zhang, Dr. Wei Yun Zhang, Dr. Huaizhi Kang and Prof. Chaoyong James Yang

      Version of Record online: 15 JUL 2011 | DOI: 10.1002/chem.201101353

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      Beacon of light! A new type of probe called an allosteric molecular beacon (aMB) has been designed for highly sensitive detection of nucleic acids, proteins, and small molecules. The aMB is designed in such way that target binding will activate its binding affinity to streptavidin microbeads for probe signal enrichment, noise reduction, and signal readout, which enables ultrasensitive target detection in complex biological samples (see scheme).

    5. Core–Shell Catalyst

      Active Site Design in a Core–Shell Nanostructured Catalyst for a One-Pot Oxidation Reaction (pages 9047–9051)

      Shusuke Okada, Dr. Kohsuke Mori, Dr. Takashi Kamegawa, Prof. Dr. Michel Che and Prof. Dr. Hiromi Yamashita

      Version of Record online: 8 JUL 2011 | DOI: 10.1002/chem.201101241

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      Designing an active site: A new type of core–shell structured catalyst was prepared, with a uniform SiO2 core supporting Pd nanoparticles (NPs) covered with a Ti-containing mesoporous silica shell. Generated H2O2 on the inner Pd NP site could interact with the Ti oxide moieties within the mesopores before dispersion to the solvent can occur, which ultimately enhances the oxidation activity for one-pot oxidation of sulfide to sulfoxide.

    6. Click Chemistry

      Click Chemistry for the Assembly of Gold Nanorods and Silver Nanoparticles (pages 9052–9056)

      Erica Locatelli, Dr. Guido Ori, Dr. Marc Fournelle, Dr. Robert Lemor, Dr. Monia Montorsi and Dr. Mauro Comes Franchini

      Version of Record online: 8 JUL 2011 | DOI: 10.1002/chem.201101027

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      Click chemistry based on a 1,3-dipolar cycloaddition between lipophilic gold nanorods (GNRs) containing an acetylene group with spherical silver nanoparticles containing an azide has been accomplished (see scheme). Phantom experiments show that this organic transformation did not affect the suitability of the gold nanorods as contrast agents for optoacoustic imaging.

    7. Mesoporous Materials

      General Synthesis of Hybrid TiO2 Mesoporous “French Fries” Toward Improved Photocatalytic Conversion of CO2 into Hydrocarbon Fuel: A Case of TiO2/ZnO (pages 9057–9061)

      Dr. Guangcheng Xi, Dr. Shuxin Ouyang and Prof. Jinhua Ye

      Version of Record online: 8 JUL 2011 | DOI: 10.1002/chem.201100580

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      From fries to fuel! Reduction of CO2 from a waste combustion product into a hydrocarbon fuel using solar energy is one of the best strategies to manage global warming and energy shortage. Homogeneously hybrid TiO2/ZnO mesoporous “french fries” (MFFs) were synthesized by a facile furfural alcohol-derived polymerization–oxidation route (see scheme). The unusual hybrid mesoporous structure of the TiO2/ZnO MFFs enhances the photocatalytic activity toward conversion of CO2 into hydrocarbon fuel (CH4) in the presence of water vapor.

    8. Cycloaddition

      RhI-Catalyzed [6+2] Cycloaddition of Alkyne–Allenylcyclobutanes: A New Entry for the Synthesis of Bicyclo[6.m.0] Skeletons (pages 9062–9065)

      Dr. Fuyuhiko Inagaki, Katsuya Sugikubo, Yuki Oura and Prof. Dr. Chisato Mukai

      Version of Record online: 15 JUL 2011 | DOI: 10.1002/chem.201101441

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      Bicyclo under construction! The [RhCl(dppp)2]-catalyzed intramolecular [6+2] cycloisomerization of alkyne–allenylcyclobutanes efficiently produced bicyclo[6.4.0]dodecatriene and bicyclo[6.3.0]undecatriene skeletons (see scheme). Straightforward cleavage of the unfunctionalized simple cyclobutane and construction of the bicyclo[6.m.0] frameworks could be achieved under mild conditions.

    9. Sensors

      Ratio-Au: A FRET-based Fluorescent Probe for Ratiometric Determination of Gold Ions and Nanoparticles (pages 9066–9069)

      Xiaowei Cao, Prof. Weiying Lin and Yundi Ding

      Version of Record online: 15 JUL 2011 | DOI: 10.1002/chem.201003586

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      Digging for gold: Ratio-Au—the first ratiometric fluorescent probe for Au3+ based on fluorescence (or Förster) resonance energy transfer—has been judiciously designed and synthesized on the basis of the newly discovered Au3+-mediated transformation of thioamide-phenyl-substituted alkynes to 5-ketothiazoles (see scheme).

    10. Gold Catalysis

      Gold(I)-Catalyzed Tandem Oxidative Ring-Opening/C[BOND]C Bond Cleavage Reactions of Vinylidenecyclopropanes with Secondary Amines Under an Oxygen Atmosphere (pages 9070–9075)

      Bei-Li Lu and Prof. Dr. Min Shi

      Version of Record online: 8 JUL 2011 | DOI: 10.1002/chem.201100862

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      A Midas touch! Gold(I)-catalyzed tandem oxidative ring-opening/C[BOND]C bond cleavage reactions of vinylidenecyclopropanes with a variety of secondary amines proceeded smoothly in toluene or 1,1,2,2-tetrachloroethane (TCE) to give the corresponding amides in moderate to good yields under oxygen atmosphere (see scheme; DCE=1,2-dichloroethane). The scope and limitations as well as the plausible mechanisms have been discussed.

  7. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
    1. Light-Emitting Diodes

      High-Efficiency Tris(8-hydroxyquinoline)aluminum (Alq3) Complexes for Organic White-Light-Emitting Diodes and Solid-State Lighting (pages 9076–9082)

      Dr. César Pérez-Bolívar, Dr. Shin-ya Takizawa, Dr. Go Nishimura, Dr. Victor A. Montes and Prof. Dr. Pavel Anzenbacher Jr.

      Version of Record online: 21 JUL 2011 | DOI: 10.1002/chem.201100707

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      Whiter than white: Electron-withdrawing and -donating substituents on the tris(8-hydroxyquinoline)AlIII (Alq3) complexes allow for control of the emission and electroluminescence from green (526 nm) to the blue region (487 nm), and of the fluorescence quantum yield (0.15–0.57). The compounds used as emitters in OLEDs show a maximum external quantum efficiency (EQE) of 4.6 %, which is among the highest observed for Alq3 complexes. The complexes were used in white-light emitting OLEDs achieving high efficiency (EQE ≈19 %) and high white color purity (CRI≈85).

    2. Hydrocarbons

      Theoretical Simulations Elucidate the Role of Naphthalenic Species during Methanol Conversion within H-SAPO-34 (pages 9083–9093)

      Dr. Karen Hemelsoet, Arno Nollet, Prof. Dr. Veronique Van Speybroeck and Prof. Dr. Michel Waroquier

      Version of Record online: 19 JUL 2011 | DOI: 10.1002/chem.201100920

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      Bit on the side! Calculated intrinsic activation barriers of successive methylations of naphthalenic compounds in H-SAPO-34 are relatively independent of the number of methyl groups already attached on the aromatic and are on average 140 kJ mol−1 (see scheme). An alternative side-chain methylation was found to exhibit a high barrier and hence is not expected to be an active ethene-eliminating route.

    3. Neutron Scattering

      Inelastic Neutron Scattering on an Mn10 Supertetrahedron: Assessment of Exchange Coupling Constants, Ferromagnetic Spin Waves and an Analogy to the Hückel Method (pages 9094–9106)

      Stefan Stuiber, Dr. Gang Wu, Joscha Nehrkorn, Dr. Jan Dreiser, Dr. Yanhua Lan, Dr. Ghenadie Novitchi, Dr. Christopher E. Anson, Dr. Tobias Unruh, Prof. Dr. Annie K. Powell and Prof. Dr. Oliver Waldmann

      Version of Record online: 5 JUL 2011 | DOI: 10.1002/chem.201100500

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      Spin-wave theory for chemists! The synthesis, crystal structure and magnetism of an Mn10 supertetrahedron is reported (see figure). Inelastic neutron scattering and magnetic data permit the accurate determination of the ferromagnetic exchange coupling constants. An analogy to the Hückel method can be drawn, which allows one to understand the results of the spin-wave theory, that is, magnetic excitation spectrum in a chemical language.

    4. Surface Chemistry

      Chemical Surface Modification of Self-Assembled Monolayers by Radical Nitroxide Exchange Reactions (pages 9107–9112)

      Hendrik Wagner, Dr. Marion K. Brinks, Dr. Dr. Michael Hirtz, Dr. Andreas Schäfer, Prof. Dr. Lifeng Chi and Prof. Dr. Armido Studer

      Version of Record online: 5 JUL 2011 | DOI: 10.1002/chem.201100543

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      A radical exchange: Chemical modification of silicon surfaces with alkoxyamine-based self-assembled monolayers (SAMs) was achieved by reversible radical nitroxide exchange reactions. The covalent immobilization of various substrates is possible by this approach (see scheme; X=dyes, sugars, peptide or biotin). A prestructured SAM was prepared by Langmuir–Blodgett lithography and successfully used in the nitroxide exchange reaction for site-selective chemical surface modification.

    5. Ionic Liquids

      Lanthanide Ion Extraction by Trifluoromethyl-1,3-diketonate-Functionalised Ionic Liquids Adsorbed on Silica (pages 9113–9122)

      Jean-Hubert Olivier, Dr. Franck Camerel and Prof. Raymond Ziessel

      Version of Record online: 7 JUL 2011 | DOI: 10.1002/chem.201100296

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      Task-specific ionic liquids carrying trifluoromethyl-1,3-diketonate moieties have been designed and used for efficient extraction of EuIII and TbIII from aqueous solutions (see picture). The luminescence properties of the complexes formed can be used to follow the extraction process.

    6. Cyanide Receptors

      From Atomic to Molecular Anions: A Neutral Receptor Captures Cyanide Using Strong C[BOND]H Hydrogen Bonds (pages 9123–9129)

      Raghunath O. Ramabhadran, Yuran Hua, Yong-jun Li, Prof. Amar H. Flood and Prof. Krishnan Raghavachari

      Version of Record online: 27 JUN 2011 | DOI: 10.1002/chem.201100793

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      Two for one: The diatomic cyanide anion binds as strong as monoatomic chloride by engaging hydrogen bonds with the C[BOND]H groups located inside the rigid cavities of triazolophanes (see figure).

    7. Structure Elucidation

      Simultaneous End-On/Side-On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre-organization of Oligometallic CuI Acceptors (pages 9130–9141)

      Dr. Stefan Welsch, Dr. Christophe Lescop, Dr. Gabor Balazs, Prof. Régis Réau and Prof. Dr. Manfred Scheer

      Version of Record online: 1 JUL 2011 | DOI: 10.1002/chem.201100845

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      One way or another: Reactions with pre-organized CuI bi- and trimetallic precursors changed the coordination abilities of the organometallic P2 ligand complex [{CpMo(CO)2}2(μ,η22-P2)] (see figure). Unprecedented simultaneous end-on/side-on coordination modes were identified that reflected the behavior of the heavier Sb2 homologue.

    8. Isolobal Analogy

      Structure and Bonding in Stannadiphospholes and their Dianions SnC2P2R2m (R=H, tBu m=0, −2): A Comparative Study with C5H5+ and C5H5 Analogues (pages 9142–9152)

      K. Harikrishna Reddy, Dr. Dandamudi Usharani, Prof. John F. Nixon and Prof. Eluvathingal D. Jemmis

      Version of Record online: 15 JUL 2011 | DOI: 10.1002/chem.201100239

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      Tin–carbon analogy: The isolobal relationship between carbon and its heavier congener tin has been analysed by the study of the potential energy surfaces of neutral and dianionic SnC2P2R2 (R=H, tBu, see figure). The results show that major roles are played by 3D aromaticity in the case of neutral isomers and by 2D aromaticity in the case of dianionic isomers. Comparison of stannadiphospholes with other heterodiphospholes indicates that Sn might be a better isolobal analogue to P+ than to BH or CH+.

    9. Photophysics

      Synthesis and Photophysics of Silicon Phthalocyanine–Perylenebisimide Triads Connected through Rigid and Flexible Bridges (pages 9153–9163)

      F. Javier Céspedes-Guirao, Dr. Luis Martín-Gomis, Dr. Kei Ohkubo, Prof. Dr. Shunichi Fukuzumi, Prof. Dr. Fernando Fernández-Lázaro and Prof. Dr. Ángela Sastre-Santos

      Version of Record online: 28 JUN 2011 | DOI: 10.1002/chem.201100320

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      Molecular architectures: The photoinduced electron-transfer processes in three new silicon phthalocyanine (SiPc)–perylenebisimide (PBI) triads are investigated. The differences in the photophysics of the triads (see figure) demonstrate the importance of the rigidity of the spacer and the orientation between donor and acceptor units.

    10. Immunoassays

      Towards Libraries of Luminescent Lanthanide Complexes and Labels from Generic Synthons (pages 9164–9179)

      Dr. Matthieu Starck, Dr. Pascal Kadjane, Dr. Emmanuel Bois, Dr. Bruno Darbouret, Dr. Anne Incamps, Dr. Raymond Ziessel and Dr. Loïc J. Charbonnière

      Version of Record online: 1 JUL 2011 | DOI: 10.1002/chem.201100390

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      A synthetic strategy to produce a large number of luminescent lanthanide complexes of europium and terbium from generic synthons has been developed. The strategy is further derived to produce activated complexes that can be labelled on beads or biomolecules, and that have been applied to a time-resolved fluoroimmunoassay for the detection of carcinoembryonic antigenes.

    11. Blue Phosphorescence

      Design and Synthesis of Iridium Bis(carbene) Complexes for Efficient Blue Electrophosphorescence (pages 9180–9187)

      Dr. Cheng-Han Hsieh, Dr. Fang-Iy Wu, Chun-Hsiang Fan, Min-Jie Huang, Kun-Yi Lu, Pei-Yu Chou, Yu-Han Ou Yang, Shih-Hsiang Wu, Prof. Dr. I-Chia Chen, Shu-Hua Chou, Prof. Dr. Ken-Tsung Wong and Prof. Dr. Chien-Hong Cheng

      Version of Record online: 5 JUL 2011 | DOI: 10.1002/chem.201100317

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      Simple and effective! Experimental and theoretical studies show that the emissive state of the iridium complexes (see figure) is mainly controlled by the single conjugated N,N′-heteroaromatic ligand. Their emission color can be systematically tuned from light to deep blue by simple ligand modulation. The blue electrophosphorescent devices using these complexes as the emitter show very high external quantum efficiencies of 7.6–15.2 %.

    12. Sustainable Energy

      Generating Hydrogen Gas from Methane with Carbon Captured as Pure Spheroidal Nanomaterials (pages 9188–9192)

      Andrew Cornejo, Weike Zhang, Prof. Lizhen Gao, Rahi R. Varsani, Prof. Martin Saunders, Dr. K. Swaminathan Iyer, Prof. Colin L. Raston and Prof. Hui Tong Chua

      Version of Record online: 5 JUL 2011 | DOI: 10.1002/chem.201100532

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      Methane cracking: A highly effective strategy for the production of hydrogen fuel and carbon from methane gas with zero emission, which is free of CO2 and CO, has been developed, with the carbon captured as graphitic spheroidal carbon that encapsulates catalytic particles (see scheme). A practical method for removing the catalytic particles has been developed, transforming the material into essentially pure spheroidal carbon.

    13. Homoaromaticity

      The Experimental Realization of a Neutral Homoaromatic Carbocycle (pages 9193–9199)

      Prof. Peter R. Griffiths, Dr. Don E. Pivonka and Prof. Richard Vaughan Williams

      Version of Record online: 6 JUL 2011 | DOI: 10.1002/chem.201100025

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      The bisannelated semibullvalene depicted is demonstrated to be a ground-state-neutral homoaromatic carbocycle through vapor-phase infrared spectroscopy.

    14. Halocompounds

      Synthetic Utilization of 2-Chloro-1,1,1,2-tetrafluoroethane (pages 9200–9208)

      Keiji Notsu, Dr. Yasuyuki Zushi, Shin Ota, Dr. Tomoko Kawasaki-Takasuka and Dr. Takashi Yamazaki

      Version of Record online: 5 JUL 2011 | DOI: 10.1002/chem.201100900

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      Get someZ's! β-Substituted α-fluoro-α,β-unsaturated carboxylic acids have been successfully synthesized from 2-chloro-1,1,1,2-tetrafluoroethane, one of the major byproducts of tetrafluoroethene formation from chlorofluoromethane. The products are usually obtained with Z stereoselectivity, by either a stepwise or a one-pot three-step procedure (see scheme).

    15. Single-Molecule Magnets

      Structure, Magnetism and Theory of a Family of Nonanuclear CuII5LnIII4–Triethanolamine Clusters Displaying Single-Molecule Magnet Behaviour (pages 9209–9218)

      Dr. Stuart K. Langley, Dr. Liviu Ungur, Nicholas F. Chilton, Dr. Boujemaa Moubaraki, Prof. Liviu F. Chibotaru and Prof. Keith S. Murray

      Version of Record online: 5 JUL 2011 | DOI: 10.1002/chem.201100218

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      Bow ties are cool! A rectangle with a bow tie describes the cluster core of a family of nonanuclear, isostructural 3d–4f clusters [CuII5LnIII4O2(teaH)4{O2CC(CH3)3}2(NO3)4(OMe)4]2MeOH2Et2O [Ln=Gd (1), Tb (2), Dy (3) and Ho (4)] (see picture; Cu green, Ln purple). Complexes 24 show single-molecule magnet behaviour, and the DC susceptibility of 3 was successfully interpreted in terms of three J values obtained from ab initio calculations.

    16. Single-Molecule Studies

      The Role of Electronic Coupling in Linear Porphyrin Arrays Probed by Single-Molecule Fluorescence Spectroscopy (pages 9219–9225)

      Jaesung Yang, Ji-Eun Lee, Dr. Chang Yeon Lee, Dr. Naoki Aratani, Prof. Dr. Atsuhiro Osuka, Prof. Dr. Joseph T. Hupp and Prof. Dr. Dongho Kim

      Version of Record online: 5 JUL 2011 | DOI: 10.1002/chem.201100236

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      Effective communication: At a single-molecule level, butadiyne-linked linear porphyrin arrays with extensive π-conjugation perform as photostable one-quantum systems, whereas strong excitonic dipole coupling observed for directly-linked linear porphyrin arrays favors strong communication between porphyrins, but allows each porphyrin to maintain its individual character (see figure).

    17. TiO2 Nanoparticles

      On the Reactions of Methyl Radicals with TiO2 Nanoparticles and Granular Powders Immersed in Aqueous Solutions (pages 9226–9231)

      Olga Golberg-Oster, Ronen Bar-Ziv, Guy Yardeni, Dr. Israel Zilbermann and Prof. Dan Meyerstein

      Version of Record online: 5 JUL 2011 | DOI: 10.1002/chem.201100338

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      .CH3reacts with TiO2: Methyl radicals react with TiO2 nanoparticles (NPs) immersed in aqueous solutions to form transients in which the methyls are covalently bound to the particles. The rate constant for this reaction approaches the diffusion-controlled limit. The transients decompose to yield ethane (see figure). Rutile powders behave similarly to the TiO2 NPs, whereas the mechanism for the decomposition of the transients formed in the analogous reaction of the radicals with anatase powders differs.

    18. Metal–Organic Frameworks

      A New Coordination Polymer Exhibiting Unique 2D Hydrogen-Bonded (H2O)16 Ring Formation and Water-Dependent Luminescence Properties (pages 9232–9241)

      Prof. Chih-Chieh Wang, Ching-Chun Yang, Wen-Chun Chung, Dr. Gene-Hsiang Lee, Prof. Mei-Lin Ho, Ya-Chien Yu, Min-Wen Chung, Prof. Hwo-Shuenn Sheu, Chien-Hung Shih, Kum-Yi Cheng, Pei-Jen Chang and Prof. Pi-Tai Chou

      Version of Record online: 7 JUL 2011 | DOI: 10.1002/chem.201100176

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      Holding water: [Zn(dpe)(bdc)]4H2O (ZndB; dpe=1,2-bis(4-pyridyl)ethane, bdc2−=dianion of benzenedicarboxylic acid) has a 3D metal–organic framework constructed by the assembly of helical channels filled with guest water molecules. The resulting network creates a 2D water layer containing hydrogen-bonded (H2O)16 rings. Color changes occur upon hydration and water depletion of ZndB, accompanied by an increase in emission intensity (see figure).

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    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
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      Preview: Chem. Eur. J. 34/2011 (page 9243)

      Version of Record online: 2 AUG 2011 | DOI: 10.1002/chem.201190168

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