Chemistry - A European Journal

Cover image for Vol. 18 Issue 24

June 11, 2012

Volume 18, Issue 24

Pages 7313–7627

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Communications
    7. Full Papers
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      Cover Picture: Highly Enantioselective Epoxidation of Multisubstituted Enones Catalyzed by Non-Heme Iron Catalysts (Chem. Eur. J. 24/2012) (page 7313)

      Bin Wang, Shoufeng Wang, Prof. Dr. Chungu Xia and Prof. Dr. Wei Sun

      Article first published online: 4 JUN 2012 | DOI: 10.1002/chem.201290097

      Thumbnail image of graphical abstract

      The non-heme iron(II) complexes of N4 ligands, derived from proline and benzimidazole, exhibited an unprecedented activity and enantioselectivity for the epoxidation of a variety of di- and trisubstituted enones. X-ray analysis of the iron complex revealed that the ligand coordinated the iron center in a cis-α topology. The 18O-isotopic-labeling experiments suggest that high-valent Fe[DOUBLE BOND]O species are involved as the active oxidant in the catalytic process. For more details, see the Communication by W. Sun et al. on page 7332 ff.

  2. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
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    1. Graphical Abstract: Chem. Eur. J. 24/2012 (pages 7316–7326)

      Article first published online: 4 JUN 2012 | DOI: 10.1002/chem.201290098

  3. Corrigenda

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
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    1. You have free access to this content
      Corrigendum: Pyrrolopyrrole Cyanine Dyes: A New Class of Near-Infrared Dyes and Fluorophores (page 7326)

      Georg M. Fischer, Magnus Isomäki-Krondahl, Inigo Göttker-Schnetmann, Ewald Daltrozzo and Andreas Zumbusch

      Article first published online: 4 JUN 2012 | DOI: 10.1002/chem.201201599

      This article corrects:

      Pyrrolopyrrole Cyanine Dyes: A New Class of Near-Infrared Dyes and Fluorophores

      Vol. 15, Issue 19, 4857–4864, Article first published online: 18 MAR 2009

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    3. You have free access to this content
  4. News

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Communications
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  5. Communications

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Communications
    7. Full Papers
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    1. Enantioselective Epoxidation

      Highly Enantioselective Epoxidation of Multisubstituted Enones Catalyzed by Non-Heme Iron Catalysts (pages 7332–7335)

      Bin Wang, Shoufeng Wang, Prof. Dr. Chungu Xia and Prof. Dr. Wei Sun

      Article first published online: 13 MAY 2012 | DOI: 10.1002/chem.201200992

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      Iron(II) efficiency: The iron complexes of N4 ligands, derived from proline and benzimidazole, exhibited an unprecedented activity and enantioselectivity for the epoxidation of a variety of di- and trisubstituted enones (see scheme). This system, based on synthetic non-heme iron catalysts, provides ready access to a wide range of epoxyketones of high enantiomeric purity.

    2. Photoredox Catalysis

      [Cu(dap)2Cl] As an Efficient Visible-Light-Driven Photoredox Catalyst in Carbon–Carbon Bond-Forming Reactions (pages 7336–7340)

      Michael Pirtsch, Suva Paria, Taisuke Matsuno, Prof. Dr. Hiroyuki Isobe and Prof. Dr. Oliver Reiser

      Article first published online: 13 MAY 2012 | DOI: 10.1002/chem.201200967

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      Copper sees the light of day: [Cu(dap)2Cl] proved to be an excellent photoredox catalyst for atom-transfer radical addition reactions, as well as for allylation reactions (see scheme), providing an attractive alternative to commonly used iridium- and ruthenium-based catalysts.

    3. Computational Chemistry

      Understanding the Extraordinary Deshielding of 129Xe in a Permetallated Cryptophane by Relativistic DFT (pages 7341–7345)

      Prof. Alessandro Bagno and Dr. Giacomo Saielli

      Article first published online: 9 MAY 2012 | DOI: 10.1002/chem.201103979

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      Shift change: Relativistic ZORA DFT calculations highlight the various factors (solvent effect, spin–orbit coupling, number and type of metal centres) responsible of the extraordinarily large deshielding of xenon encapsulated in a metallated cryptophane (see figure).

    4. Liquid Crystals

      Light-Driven Phase Transition in a Cubic-Phase-Forming Binary System Composed of 4′-n-Docosyloxy-3′-nitrobiphenyl-4-carboxylic Acid and an Azobenzene Derivative (pages 7346–7350)

      Ryo Hori, Daisuke Furukawa, Prof. Dr. Katsuhiro Yamamoto and Prof. Dr. Shoichi Kutsumizu

      Article first published online: 8 MAY 2012 | DOI: 10.1002/chem.201200810

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      Binary mixtures were prepared from an azobenzene derivative and a liquid-crystal (LC) compound that exhibits smectic C (SmC) and bicontinuous cubic (Cubbi) LC phases. Reversible switching between the two phases in response to UV-light irradiation was observed. This light-driven SmC-to-Cubbi transition is the first example showing the increased dimensionality of molecular ordering with isomerization of azobenzenes (see figure).

    5. Sensors

      Fluorescent Dendron–Cyclodextrin Nanotubes with Surface Peptide Spacer as a Recyclable Sensory Platform (pages 7351–7356)

      Jeonghun Lee, Sangkyu Park, Chuda Raj Lohani, Prof. Dr. Keun-Hyeung Lee and Prof. Dr. Chulhee Kim

      Article first published online: 9 MAY 2012 | DOI: 10.1002/chem.201200525

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      Nanotube sensory platform: Dendron–cyclodextrin nanotubes with a surface coumarin unit attached by a GH dipeptide spacer were constructed by a combination of molecular recognition and self-assembly. These unique fluorescent nanotubes can serve as a recyclable metal ion sensory platform with high selectivity and sensitivity (see scheme).

    6. Solid-State Photodimerization

      Single-Crystal-to-Single-Crystal Transformation from 1 D Staggered-Sculls Chains to 3 D NbO-Type Metal-Organic Framework through [2+2] Photodimerization (pages 7357–7361)

      Yong-Cong Ou, Da-Shuai Zhi, Wen-Ting Liu, Dr. Zhao-Ping Ni and Prof. Dr. Ming-Liang Tong

      Article first published online: 8 MAY 2012 | DOI: 10.1002/chem.201200226

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      A new approach to synthesize 3D structures through a [2+2] photodimerization process has been carried out by transforming two isostructures of 1D staggered-sculls chains [M(1,2-chdc)(bpe)2(H2O)2]⋅H2O (M=Zn, Mn) into 3D NbO-type metal–organic frameworks through UV irradiation in single-crystal-to-single-crystal mode. (see figure; bpe=trans-1,2-(bis(4-pyridyl)ethene, chdc=cyclohexanedicarboxylate).

    7. Domino Reactions

      Phosphine-Mediated Domino Benzannulation Strategy for the Construction of Highly Functionalized Multiaryl Skeletons (pages 7362–7366)

      Peizhong Xie, Prof. Dr. You Huang and Prof. Dr. Ruyu Chen

      Article first published online: 9 MAY 2012 | DOI: 10.1002/chem.201200305

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      A skeleton crew: A phosphine-mediated domino benzannulation strategy was developed for the synthesis of multiaryl skeletons (see scheme). A wide range of aromatic compounds and functional groups can be assembled into a multiaryl molecule through a core domino process.

    8. Polymers

      Construction of a Porous Homochiral Coordination Polymer with Two Types of CunIn Alternating Units Linked by Quinine: A Solvothermal and a Mechanochemical Approach (pages 7367–7371)

      Daniel Prochowicz, Dr. Iwona Justyniak, Dr. Arkadiusz Kornowicz, Tomasz Kaczorowski, Prof. Dr. Zbigniew Kaszkur and Prof. Dr. Janusz Lewiński

      Article first published online: 10 MAY 2012 | DOI: 10.1002/chem.201200236

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      The polymer network: The reaction of quinine (QN) with CuI under solvothermal, as well as liquid-assisted grinding, conditions afforded a unique 1D homochiral coordination polymer {[Cu43-I)4(QN)2][Cu33-I)22-I)(QN)2]2}n, containing both triangular Cu3I3 and cubane Cu4I4 clusters as connecting nodes (see scheme). Van der Waals interactions between the adjacent 1D polymer chains lead to an extended quasi-honeycomb homochiral pillared 3D network with solvent-free 1D channels.

    9. Interfacial PCET

      Proton-Coupled O2 Reduction Reaction Catalysed by Cobalt Phthalocyanine at Liquid/Liquid Interfaces (pages 7372–7376)

      Yan Li, Suozhu Wu and Dr. Bin Su

      Article first published online: 9 MAY 2012 | DOI: 10.1002/chem.201200191

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      Pushed over the edge: Proton-transfer coupled O2 reduction catalysed by cobalt phthalocyanine ([CoPc]) was studied at the water/1,2-dichloroethane (DCE) interface (see figure). This system represents a new model of molecular electrocatalysis with the proton transfer controlled by the Galvani potential difference and the electron transfer by the molecular properties of the catalyst and electron donor.

    10. Ratiometric Detection

      Salicylic-Acid Derivatives as Antennae for Ratiometric Luminescent Probes Based on Lanthanide Complexes (pages 7377–7381)

      Takuya Terai, Hiroki Ito, Prof. Dr. Kazuya Kikuchi and Prof. Dr. Tetsuo Nagano

      Article first published online: 9 MAY 2012 | DOI: 10.1002/chem.201200610

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      Long-lived ratiometric sensors: Luminescent lanthanide complexes are widely used in time-resolved assays of biomolecules, but most of the sensors with these complexes rely on single-point intensity measurements. Herein, we introduce a simple strategy to create ratiometric probes by using salicylic-acid derivatives as the antenna moiety of Tb3+ complexes. As an example, a probe for alkaline phosphatase (ALP) was developed (see scheme).

    11. Fullerenes

      Weakly Interacting Molecular Layer of Spinning C60 Molecules on TiO2 (110) Surfaces (pages 7382–7387)

      Dr. Carlos Sanchez-Sanchez, Valeria Lanzilotto, Dr. Cesar Gonzalez, Dr. Alberto Verdini, Dr. Pedro L. de Andres, Dr. Luca Floreano, Dr. Maria F. Lopez and Dr. Jose A. Martin-Gago

      Article first published online: 9 MAY 2012 | DOI: 10.1002/chem.201200627

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      The adsorption of C60, a typical acceptor organic molecule, on a TiO2 (110) surface has been investigated by a multitechnique combination, including van der Waals density functional calculations. It is shown that the adsorbed molecules form a weakly interacting molecular layer, which sits on the fivefold-coordinated Ti that is confined between the prominent bridging oxygen rows (see figure).

  6. Full Papers

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Communications
    7. Full Papers
    8. Preview
    1. Enzymatic Glycosylation

      Kinetics of Iterative Carbohydrate Transfer to Polysaccharide Catalyzed by Chondroitin Polymerase on a Highly Sensitive Flow-Type 27 MHz Quartz-Crystal Microbalance (pages 7388–7393)

      Prof. Dr. Toshiaki Mori, Takayuki Kodera, Hiroshi Yoshimine, Prof. Dr. Yoshimitsu Kakuta, Prof. Dr. Nobuo Sugiura, Prof. Dr. Koji Kimata and Prof. Dr. Yoshio Okahata

      Article first published online: 21 MAY 2012 | DOI: 10.1002/chem.201200342

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      One-sugar transfer: Kinetics of one-sugar transfer can be evaluated by using a highly sensitive flow-type quartz-crystal microbalance. Binding affinity and turnover number for UDP-GlcA and UDP-GalNAc are quite different. The catalytic efficiency is similar for GlcA transfer and GalNAc transfer (see scheme).

    2. Nanoparticles

      Magnetic Nanoparticles Entrapped in Siliceous Mesocellular Foam: A New Catalyst Support (pages 7394–7403)

      Dr. Su Seong Lee, Siti Nurhanna Riduan, Dr. Nandanan Erathodiyil, Dr. Jaehong Lim, Jian Liang Cheong, Dr. Junhoe Cha, Dr. Yu Han and Prof. Jackie Y. Ying

      Article first published online: 15 MAY 2012 | DOI: 10.1002/chem.201102361

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      Foam party: γ-Fe2O3 nanoparticles were grown inside siliceous mesocellular foams (MCFs), which retained a high surface area and a large pore size. The MCFs facilitated the recovery of enzyme catalysts, Pd nanoclusters, and Ru-based catalysts (see figure).

    3. Donor–Acceptor Systems

      Encapsulation of TCNQ and the Acridinium Ion within a Bisporphyrin Cavity: Synthesis, Structure, and Photophysical and HOMO–LUMO-Gap-Mediated Electron-Transfer Properties (pages 7404–7417)

      Arvind Chaudhary and Dr. Sankar Prasad Rath

      Article first published online: 8 MAY 2012 | DOI: 10.1002/chem.201200034

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      Donor–acceptor complexes, which were constructed from free base bisporphyrin (H4DEP) as a host, strongly encapsulated two electron-deficient guests, TCNQ and the acridinium ion, in its clefts. The extremely low electrochemically evaluated HOMO–LUMO gap in H4DEPTCNQ led to facile electron transfer from the host to the guest at room temperature, whilst partial electron transfer took place in [H4DEPAcH]ClO4 (see figure).

    4. Fullerenes

      Crystal-Packing Trends for a Series of 6,9,12,15,18-Pentaaryl-1-hydro[60]fullerenes (pages 7418–7433)

      Dr. Robert D. Kennedy, Merissa Halim, Dr. Saeed I. Khan, Prof. Benjamin J. Schwartz, Prof. Sarah H. Tolbert and Prof. Yves Rubin

      Article first published online: 9 MAY 2012 | DOI: 10.1002/chem.201103400

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      Packing case: The different determinants for molecular packing found in the crystal structures of fifteen self-complementary 6,9,12,15,18-pentaaryl-1-hydro[60]fullerenes and their various solvates have been examined (see figure). The relationships between molecular structure, occluded solvents, and packing motifs and the influence on electron mobility within the fullerene phase are discussed.

    5. DNA Structures

      Additional Base-Pair Formation in DNA Duplexes by a Double-Headed Nucleotide (pages 7434–7442)

      Dr. Charlotte S. Madsen, Sarah Witzke, Dr. Pawan Kumar, Dr. Kushuma Negi, Prof. Dr. Pawan K. Sharma, Prof. Dr. Michael Petersen and Prof. Dr. Poul Nielsen

      Article first published online: 24 APR 2012 | DOI: 10.1002/chem.201103467

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      Two heads are better than one! We show that a double-headed nucleotide that presents two nucleobases in a DNA duplex recognises and forms Watson–Crick base pairs with two complementary adenines (see figure). Furthermore, with judicious positioning, the nucleotide recognises itself through the formation of a T:T pair. These nucleic acid motifs extend the DNA recognition repertoire and may form the basis for a complete series of double-headed nucleotides based on all 16 base combinations of the four natural nucleobases.

    6. Electrocatalysts

      Small-Sized and Contacting Pt–WC Nanostructures on Graphene as Highly Efficient Anode Catalysts for Direct Methanol Fuel Cells (pages 7443–7451)

      Dr. Ruihong Wang, Dr. Ying Xie, Dr. Keying Shi, Dr. Jianqiang Wang, Dr. Chungui Tian, Prof. Peikang Shen and Prof. Honggang Fu

      Article first published online: 30 APR 2012 | DOI: 10.1002/chem.201103011

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      A ternary electrocatalyst consisting of small-sized and contacting Pt–WC nanostructures on graphene (see figure) was designed and prepared. Compared to Pt/graphene and commercial catalysts, the Pt–WC/graphene electrocatalyst exhibits higher mass activity and stability due to its superior synergistic effect, highly dispersed, well-crystallized catalyst particles, and the combined functions of the three constituents (Pt, WC, and graphene).

    7. Natural Products

      Total Synthesis of Bistramide A and Its 36(Z) Isomers: Differential Effect on Cell Division, Differentiation, and Apoptosis (pages 7452–7466)

      Dr. Loïc Tomas, Dr. Gustav Boije af Gennäs, Dr. Marie Aude Hiebel, Dr. Peter Hampson, Dr. David Gueyrard, Dr. Béatrice Pelotier, Prof. Jari Yli-Kauhaluoma, Prof. Olivier Piva, Prof. Janet M. Lord and Prof. Peter G. Goekjian

      Article first published online: 26 APR 2012 | DOI: 10.1002/chem.201102462

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      Actin versus apoptosis–not so EZ: The total synthesis of bistramide A and its 36(Z),39(S) and 36(Z),39(R) isomers (see figure) relies on a novel synthesis of exocyclic enol ethers for the spiroketal fragment, a kinetic oxa-Michael cyclization for the tetrahydropyran fragment, and an asymmetric crotonylation for the amino acid fragment. These compounds show distinctly different effects on cell division, differentiation, and apoptosis, thus suggesting that there are multiple independent biological activities of the natural product.

    8. Nanoparticles

      Surface-Plasmon-Enhanced Band Emission of ZnO Nanoflowers Decorated with Au Nanoparticles (pages 7467–7472)

      Saji Thomas Kochuveedu, Ji Hye Oh, Prof. Young Rag Do and Prof. Dong Ha Kim

      Article first published online: 3 MAY 2012 | DOI: 10.1002/chem.201200054

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      Nanoflowers in the window: Band emission was enhanced through the transfer of defect emission based on the energy match between the defect emission of ZnO and the surface-plasmon excitation of Au nanoparticles (NPs) in the hybrid system consisting of ZnO nanoflowers decorated with Au NPs (see figure).

    9. Energy Transfer

      Photoinduced Energy and Electron Transfer in Phenylethynyl-Bridged Zinc Porphyrin–Oligothienylenevinylene–C60 Ensembles (pages 7473–7485)

      Dr. Maxence Urbani, Dr. Kei Ohkubo, Dr. D. M. Shafiqul Islam, Prof. Dr. Shunichi Fukuzumi and Prof. Dr. Fernando Langa

      Article first published online: 3 MAY 2012 | DOI: 10.1002/chem.201102260

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      Bridge over troubled waters: Photoinduced charge separation occurred in an electron donor–bridge–acceptor tetrad, which incorporated C60 and two porphyrin groups that were covalently linked through a phenylethynyl oligothienylenevinylene bridge, by ultrafast energy transfer from the photoexcited porphyrin to C60 (EnT).

    10. Asymmetric Catalysis

      CuII-Catalyzed Asymmetric Hydrosilylation of Diaryl- and Aryl Heteroaryl Ketones: Application in the Enantioselective Synthesis of Orphenadrine and Neobenodine (pages 7486–7492)

      Yao-Zong Sui, Xi-Chang Zhang, Jun-Wen Wu, Shijun Li, Ji-Ning Zhou, Min Li, Prof. Dr. Wenjun Fang, Prof. Dr. Albert S. C. Chan and Prof. Dr. Jing Wu

      Article first published online: 9 MAY 2012 | DOI: 10.1002/chem.201200379

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      Could do with a copper: The Cu-catalyzed conversion of diaryl- and aryl heteroaryl ketones into their corresponding alcohols proceeded in high yields and with good to excellent ee values. This process was used in the asymmetric synthesis of two anti histamines.

    11. Chiral Rotoxanes

      High-Yield Diastereoselective Synthesis of Planar Chiral [2]- and [3]Rotaxanes Constructed from per-Ethylated Pillar[5]arene and Pyridinium Derivatives (pages 7493–7500)

      Dr. Tomoki Ogoshi, Daiki Yamafuji, Takamichi Aoki, Keisuke Kitajima, Prof. Tada-aki Yamagishi, Yoshihiro Hayashi and Dr. Susumu Kawauchi

      Article first published online: 27 APR 2012 | DOI: 10.1002/chem.201200122

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      Wheels in motion: Planar chiral [2]- and [3]rotaxanes constructed from pillar[5]arenes as wheels and pyridinium derivatives as axles (see figure) were obtained in high yield using click reactions. The procedure developed in this study is a starting point for the creation of pillar[5]arene-based interlocked molecules.

    12. 13C NMR Integration

      Deuterium Quantification through Deuterium-Induced Remote 1H and 13C NMR Shifts (pages 7501–7505)

      Prof. Dr. Rudolf Knorr and Dr. David S. Stephenson

      Article first published online: 8 MAY 2012 | DOI: 10.1002/chem.201102865

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      Simple 2H isotope analyses: The series of concordant % C(CD3)3 values in this example was obtained from pairs of NMR signals separated by deuterium-induced local chemical shifts (see figure). The pertinent 13C or 1H integral ratios were determined with good reliability because they belonged to molecular positions (indicated by the arrows) that were sufficiently remote from the deuterium atoms, so that the 13C spectra could be run with a tiny relaxation delay and continuous broadband decoupling.

    13. Reactive Intermediates

      Pivaloylmetals (tBu-COM: M=Li, MgX, K) as Equilibrium Components (pages 7506–7515)

      Prof. R. Knorr, Dr. G. Böhrer, Dr. B. Schubert and P. Böhrer

      Article first published online: 13 APR 2012 | DOI: 10.1002/chem.201102867

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      NMR-invisible intermediates pivaloylmagnesium, -lithium, or -potassium, have been generated through the novel, reversible heterolytic C[BOND]C bond cleavage of the overcrowded alkoxides of the parent tri-tert-butyl acyloin. Their interception by protonation or by ketones reveals that a common initial fission step limits the overall rate (see scheme).

    14. Orbital Splitting

      Silicon-Containing Formal 4π-Electron Four-Membered Ring Systems: Antiaromatic, Aromatic, or Nonaromatic? (pages 7516–7524)

      Yun-Fang Yang, Gui-Juan Cheng, Dr. Jun Zhu, Dr. Xinhao Zhang, Dr. Shigeyoshi Inoue and Prof. Dr. Yun-Dong Wu

      Article first published online: 24 APR 2012 | DOI: 10.1002/chem.201103443

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      A character study: A DFT study has been performed to understand the intrinsic antiaromatic character of two silicon-containing formal 4π-electron four-membered ring compounds. The monoanionic bidentate ligand, amidinate, causes π-orbital splitting by interacting with the conjugated π system (see figure).

    15. Hierarchical Nanostructures

      Hierarchical TiO2 Nanospheres with Dominant {001} Facets: Facile Synthesis, Growth Mechanism, and Photocatalytic Activity (pages 7525–7532)

      Hongmei Li, Prof. Yangsu Zeng, Prof. Tongcheng Huang, Prof. Lingyu Piao, Dr. Zijie Yan and Dr. Min Liu

      Article first published online: 12 APR 2012 | DOI: 10.1002/chem.201103087

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      A one-pot hydrothermal method was used for facile synthesis of hierarchical TiO2 nanospheres with controlled surface morphologies and up to 78 % {001} facets (see figure). The influence of reaction temperature, reaction time, and HF concentration was systematically studied. A possible growth mechanism of the hierarchical TiO2 nanostructures with exposed {001} facets was proposed. Owing to their hierarchical architecture and high percentage of exposed {001} facets, the hierarchical TiO2 nanospheres exhibit much enhanced photocatalytic efficiency (almost fourfold) compared to P25 TiO2.

    16. Molecular Janus Host

      Janus-Like Squaramide-Based Hosts: Dual Mode of Binding and Conformational Transitions Driven by Ion-Pair Recognition (pages 7533–7542)

      Dr. Bartomeu Soberats, Luis Martínez, Elena Sanna, Angel Sampedro, Prof. Carmen Rotger and Prof. Antoni Costa

      Article first published online: 24 APR 2012 | DOI: 10.1002/chem.201103345

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      Two-faced hosts! Tripodal squaramide-based hosts form host–guest complexes with NR4I compounds with stoichiometries of 1:1 to 1:3 (see scheme). However, in the presence of ammonium trimesoate compounds, the same host drastically changes its conformation to form a distinct 1:1 complex with the trimesoate anion. This property has been used to drive a controlled conformational transition of the host.

    17. Photocatalysis

      Site-Selected Doping of Upconversion Luminescent Er3+ into SrTiO3 for Visible-Light-Driven Photocatalytic H2 or O2 Evolution (pages 7543–7551)

      Jinwen Shi, Prof. Dr. Jinhua Ye, Lijing Ma, Dr. Shuxin Ouyang, Dr. Dengwei Jing and Prof. Dr. Liejin Guo

      Article first published online: 24 APR 2012 | DOI: 10.1002/chem.201102807

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      Erbium-doped SrTiO3: Er3+ absorbs visible light to generate high-energy excited states by upconversion processes and local internal fields promoted energy transfer from the high-energy excited states of Er3+ in distorted BO6 octahedra to excite the host SrTiO3 (see figure). Consequently, erbium-doped SrTiO3 species with B-site occupancy instead of A-site occupancy were validated as being novel, stable, and efficient photocatalysts for visible-light-driven H2 or O2 evolution.

    18. Photochemistry

      Enantioselective Intramolecular [2+2] Photocycloaddition Reactions of 4-Substituted Coumarins Catalyzed by a Chiral Lewis Acid (pages 7552–7560)

      Richard Brimioulle, Dr. Hao Guo and Prof. Dr. Thorsten Bach

      Article first published online: 26 APR 2012 | DOI: 10.1002/chem.201104032

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      New frontiers: Lewis acid coordination opens a new access to enantiomerically enriched [2+2] photocycloaddition products. Coumarins 1 (X=CH2, CMe2, O, NBoc, NZ, NTs) react in the presence of oxazaborolidine-based Lewis acid 2 to give the tetracyclic products 3, which are obtained as single diastereosiomers in high yields and with significant enantioselectivity (74–90 % ee).

    19. Nanostructures

      One-Step Synthesis of SnO2 and TiO2 Hollow Nanostructures with Various Shapes and Their Enhanced Lithium Storage Properties (pages 7561–7567)

      Dr. Zhiyu Wang, Zi Chen Wang, Prof. Srinivasan Madhavi and Prof. Xiong Wen (David) Lou

      Article first published online: 26 APR 2012 | DOI: 10.1002/chem.201103842

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      Taking shape: A general one-step approach for the synthesis of SnO2 and TiO2 hollow nanostructures includes templating against shape-controlled Fe2O3 crystals with diverse dimensions. Benefiting from unique structural characteristics, the SnO2 hollow particles (see figure) exhibit stable capacities of around 600–700 mAh g−1 over 50 cycles when evaluated as anode materials for lithium-ion batteries.

    20. Graphene

      A First-Principles Study on the Interaction between Alkyl Radicals and Graphene (pages 7568–7574)

      Dr. Pablo A. Denis and Dr. Federico Iribarne

      Article first published online: 24 APR 2012 | DOI: 10.1002/chem.201103711

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      Students of radicals: Graphene–alkyl-radical interactions were studied by means of dispersion-corrected DFT. The results indicate that isolated alkyl radicals are not likely to be attached onto perfect graphene. It was found that the noncovalent adsorption energies computed for some radicals are much larger than the covalent binding energies (see figure), which are low.

    21. Gels

      Optically Transparent Hydrogels from an Auxin–Amino-Acid Conjugate Super Hydrogelator and its Interactions with an Entrapped Dye (pages 7575–7581)

      Amarendar Reddy, Aashish Sharma and Dr. Aasheesh Srivastava

      Article first published online: 24 APR 2012 | DOI: 10.1002/chem.201103757

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      Flexible gels better: An amide conjugate of 1-naphthaleneacetic acid and L-phenylalanine (Mw=333 Da) was as an exceptional hydrogelator owing to the flexibility of the aromatic residues. The entrapment of fluorescent dyes yielded highly fluorescent gels (see figure).

    22. Nitroxide Radicals

      Computational Design of Cyclic Nitroxides as Efficient Redox Mediators for Dye-Sensitized Solar Cells (pages 7582–7593)

      Ganna Gryn'ova, Jonathan M. Barakat, Dr. James P. Blinco, Prof. Steven E. Bottle and Prof. Michelle L. Coote

      Article first published online: 25 APR 2012 | DOI: 10.1002/chem.201103598

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      Oxidation potentials of cyclic nitroxides in acetonitrile have been calculated for a wide variety of structural motifs (see figure). Based on the results obtained, a number of reversibly oxidized compounds with equation image in a range (0.600–0.850 V vs. SHE) suitable for use as effective redox mediators in dye-sensitized solar cells (DSSCs) are proposed.

    23. Nanosheets

      The Molecularly Controlled Synthesis of Ordered Bi-dimensional C60 Arrays (pages 7594–7600)

      Dr. Régis Y. N. Gengler, Prof. Dr. Dimitrios Gournis, Akfiny H. Aimon, Dr. Luminita M. Toma and Prof. Dr. Petra Rudolf

      Article first published online: 20 APR 2012 | DOI: 10.1002/chem.201103528

      Thumbnail image of graphical abstract

      Up, up, and array: A new bottom-up approach, which combines self-assembly with the Langmuir–Schaefer technique, uses clay nanosheets as a template for the grafting of C60 into a bi-dimensional array. Cycling allows for perfect layer-by-layer growth with control at the molecular level (see figure).

    24. Composite Nanostructures

      Selectively Deposited Noble Metal Nanoparticles on Fe3O4/Graphene Composites: Stable, Recyclable, and Magnetically Separable Catalysts (pages 7601–7607)

      Xiyan Li , Xiao Wang , Shuyan Song, Dapeng Liu and Prof. Dr. Hongjie Zhang

      Article first published online: 16 APR 2012 | DOI: 10.1002/chem.201103726

      Thumbnail image of graphical abstract

      Composite nanostructures were prepared through selective deposition of Pt, Pd, or PtPd metal nanoparticles with a size of about 3–5 nm on magnetite/graphene composites by using L-lysine as linker (see figure). They are ideal recyclable catalysts, for example, for catalytic reduction of 4-nitrophenol to 4-aminophenol by NaBH4, due to their stability and efficient magnetic separation.

    25. Anion Transport

      Aggregation and Supramolecular Membrane Interactions that Influence Anion Transport in Tryptophan-Containing Synthetic Peptides (pages 7608–7623)

      Megan M. Daschbach, Saeedeh Negin, Lei You, Matthew Walsh and George W. Gokel

      Article first published online: 26 APR 2012 | DOI: 10.1002/chem.201103203

      Thumbnail image of graphical abstract

      Self-assembly versus dynamics: The work presented addresses the relationship of self-assembly and aggregation to the efficacy of Cl transport. A range of synthetic anion transporters (SATs) was prepared and their ability to transport Cl through liposomal membranes was confirmed. The general conclusion from these studies was that those compounds that self-aggregated were generally poor ion transporters. (DOPC/DOPA=1,2-dioleoyl-sn-glycero-3-phosphocholine/phosphate).

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      Preview: Chem. Eur. J. 25/2012 (page 7627)

      Article first published online: 4 JUN 2012 | DOI: 10.1002/chem.201290100

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