Chemistry - A European Journal

Cover image for Vol. 18 Issue 43

October 22, 2012

Volume 18, Issue 43

Pages 13545–13896

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    8. Corrigendum
    1. You have free access to this content
      Cover Picture: Perylene Bisimide Dimer Aggregates: Fundamental Insights into Self-Assembly by NMR and UV/Vis Spectroscopy (Chem. Eur. J. 43/2012) (page 13545)

      Changzhun Shao, Dr. Matthias Grüne, Dr. Matthias Stolte and Prof. Dr. Frank Würthner

      Version of Record online: 16 OCT 2012 | DOI: 10.1002/chem.201290187

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      Widely applied automotive color pigments based on perylene bisimide have been utilized by many groups to create extended one-dimensional π stacks by self-assembly. In their Full Paper on page 13665 ff., F. Würthner et al. report on the application of sterically demanding groups to terminate self-assembly at the dimer stage. Only in highly nonpolar aliphatic solvents, a rather unusual growth into larger self-assembled structures is observed.

    2. You have free access to this content
      Inside Cover: Spiky Mesoporous Anatase Titania Beads: A Metastable Ammonium Titanate-Mediated Synthesis (Chem. Eur. J. 43/2012) (page 13546)

      Dr. Dehong Chen, Dr. Fuzhi Huang, Lu Cao, Prof. Yi-Bing Cheng and Prof. Rachel A. Caruso

      Version of Record online: 16 OCT 2012 | DOI: 10.1002/chem.201290188

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      Spiky mesoporous anatase titania beads have been fabricated and are described in the Full Paper by R. A. Caruso et al. on page 13762 ff. These unique nanostructures were prepared through a controllable phase transformation and crystallization process from amorphous precursor beads to metastable amorphous titania/ammonium titanate core-shell structures, and then finally to anatase beads. The resultant spiky titania beads show great potential as working electrodes for high-performance dye-sensitized solar cells.

    3. You have free access to this content
      Back Cover: Solid-State 73Ge NMR Spectroscopy of Simple Organogermanes (Chem. Eur. J. 43/2012) (page 13900)

      Margaret A. Hanson, Andre Sutrisno, Victor V. Terskikh, Kim M. Baines and Yining Huang

      Version of Record online: 16 OCT 2012 | DOI: 10.1002/chem.201290191

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      Germanium-73 is an extremely challenging nucleus to examine by solid-state NMR spectroscopy, due to its unfavorable NMR properties. Through the use of an ultrahigh (21.1 T) magnetic field, a systematic study of a series of organogermanes was carried out. For details, see the Full Paper by K. M. Baines, Y. Huang et al. on page 13770 ff.

  2. Graphical Abstract

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

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

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

      f-Element–Metal Bonding and the Use of the Bond Polarity To Build Molecular Intermetalloids (pages 13566–13579)

      Dr. Benjamin Oelkers, Dr. Mikhail V. Butovskii and Prof. Dr. Rhett Kempe

      Version of Record online: 27 SEP 2012 | DOI: 10.1002/chem.201200783

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      Molecular intermetalloids: In this Concept, structurally authenticated molecular compounds with direct bonds between rare-earth metals or actinoids and transition or main-group metals are summarized. Special attention is given to the use of bond polarity as a tool for designing molecular intermetalloids incorporating rare-earth and transition metals.

  5. Communications

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

      Trityl Radicals: Spin Labels for Nanometer-Distance Measurements (pages 13580–13584)

      Gunnar W. Reginsson, Nitin C. Kunjir, Prof. Snorri Th. Sigurdsson and Prof. Olav Schiemann

      Version of Record online: 20 SEP 2012 | DOI: 10.1002/chem.201203014

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      Spin labelling with trityls: To gather information about the structure and dynamics of trityl radicals, spin-labelled polymers were measured with pulsed electron–electron double resonance (PELDOR) and double-quantum coherence (DQC). This study demonstrates that trityl radicals have great potential as spin labels that eliminate some limitations of nitroxide spin labels (see figure).

    2. Sigmatropic Rearrangements

      Reversible Cyclopropane Ring-Cleavage Reactions within Etheno-Bridged [4.3.1]Propelladiene Frameworks Leading to Aza- and Oxa-[5.6.5.6]fenestratetraenes (pages 13585–13588)

      Nora Heinrich, Dr. Anthony C. Willis, Dr. Ian A. Cade, Dr. Junming Ho, Prof. Michelle L. Coote and Prof. Martin G. Banwell

      Version of Record online: 17 SEP 2012 | DOI: 10.1002/chem.201202903

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      Opening and closing a chemical window: Oxidation of the etheno-bridged [4.3.1]propelladienol 1 with pyridinium chlorochromate (PCC) affords oxa[5.6.5.6]fenestratetraene 2. The reduction of 2 with diisobutylaluminum hydride (DIBAl-H) leads to the regeneration of its precursor (1; see scheme). These transformations most likely involve a [3,5]-sigmatropic rearrangement process.

    3. Zintl Anions

      Subtle Impact of Atomic Ratio, Charge and Lewis Basicity on Structure Selection and Stability: The Zintl Anion [(La@In2Bi11)(μ-Bi)2(La@In2Bi11)]6− (pages 13589–13595)

      Dipl.-Chem. Bastian Weinert, Dr. Florian Weigend and Prof. Dr. Stefanie Dehnen

      Version of Record online: 20 SEP 2012 | DOI: 10.1002/chem.201202369

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      Ternary intermetalloid cluster: The first intermetalloid M/13/15 Zintl anion [(La@In2Bi11)(μ-Bi)2(La@In2Bi11)]6− was obtained upon reaction of [InBi3]2− with [La(C5Me4H)3] in ethane-1,2-diamine (see scheme). DFT calculations served to analyze and explain the Lewis acid/base interaction upon assignment of formal charges as “Bi+[LEFTWARDS ARROW]In2−”, which discriminates the anion from an isoelectronic La/Sn/Bi analogue that does not require bridging.

    4. Cluster Compounds

      Synthesis and Assembly of a Difunctional Core POM Cluster with Two Appended POM Cluster Caps (pages 13596–13599)

      Dr. Jin Zhang, Panchao Yin, Dr. Jian Hao, Dr. Fengping Xiao, Liye Chen and Prof. Dr. Yongge Wei

      Version of Record online: 13 SEP 2012 | DOI: 10.1002/chem.201201098

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      A series of nanorod-like organic–inorganic hybrids based on hexamolybdate and Anderson-type heteropolyoxomolybdates has been prepared using the well-developed DCC protocol. The present work opens a way to flexibly introduce two different functional groups to a hexamolybdate ion and explore thoroughly the whole family of organoimido derivatives for fabricating novel molecular nanostructures with tunable properties (see figure).

    5. [{Fe(CO)3}4{SnI}6I4]2−: The First Bimetallic Adamantane-Like Cluster (pages 13600–13604)

      Dr. Silke Wolf, Dipl.-Chem. Florian Winter, Prof. Dr. Rainer Pöttgen, Dipl.-Chem. Nils Middendorf, Prof. Dr. Wim Klopper and Prof. Dr. Claus Feldmann

      Version of Record online: 17 SEP 2012 | DOI: 10.1002/chem.201202683

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      Show some metal: The first bimetallic adamantane-like cluster, [{Fe(CO)3}4{SnI}6I4]2− (see structure), was prepared by an ionic-liquid-based synthesis. The valence states of iron and tin were verified based on bond-length considerations, FT-IR and 119Sn Mössbauer spectroscopy, as well as with DFT calculations.

    6. Photochemistry

      A Spectroscopic and Computational Study of a Photoinduced Cross-Dehydrogenative Coupling Reaction of a Stable Semiquinone Radical (pages 13605–13608)

      Dr. Jakob Grilj, Dr. Tanya Kumanova Todorova, Dr. Chenyi Yi, Dr. Shi-Xia Liu, Prof. Eric Vauthey and Prof. Silvio Decurtins

      Version of Record online: 18 SEP 2012 | DOI: 10.1002/chem.201201463

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      Norrish-type-II reaction on a semiquinone radical: Stable semiquinone radicals serve as novel molecular platforms on which a Norrish-type-II photoreaction can be initiated. A detailed reaction scheme involving a 1,5-hydrogen transfer followed by a cyclization step that finally leads to a new C[BOND]C bond formation could be verified. Transient absorption spectroscopy and DFT calculations trace convincingly the intermediates and transition states along the reaction path (see scheme).

    7. Oxidation Reactions

      Biomimetic Oxidative Coupling of Benzylamines and 2-Aminophenols: Synthesis of Benzoxazoles (pages 13609–13613)

      Dr. Yoshinori Endo and Prof. Dr. Jan-E. Bäckvall

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/chem.201202187

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      Aerobic oxidation: In a biomimetic approach, a mixture of redox catalysts forms couples that effect the aerobic oxidation of a mixture of benzylamine and 2-aminophenol derivatives to give the corresponding benzoxazoles (see scheme). This biomimetic oxidation proceeds smoothly under mild conditions and the protocol can also be used for preparing benzimidazoles and benzothiazoles.

    8. Arylation Reactions

      Efficient Synthesis of Oxygenated Terphenyls and Other Oligomers: Sequential Arylation Reactions Through Phenol Oxidation–Rearomatization (pages 13614–13618)

      Dr. Toshifumi Dohi, Tohru Kamitanaka, Shohei Watanabe, Yinjun Hu, Naohiko Washimi and Prof. Dr. Yasuyuki Kita

      Version of Record online: 20 SEP 2012 | DOI: 10.1002/chem.201202086

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      One by one: Starting from simple phenols, a diverse series of oxygenated terphenyl compounds can be prepared in a concise and practical manner using sequential arylation reactions involving phenol oxidation/rearomatization and quinone monoacetal intermediates (see scheme). Many of the terphenyl products can be used for preparing well-defined oligomers and, furthermore, contain valuable functional groups that can be transformed for further diversification.

    9. Heterocycle Synthesis

      A General and Efficient Palladium-Catalyzed Carbonylative Synthesis of 2-Aryloxazolines and 2-Aryloxazines from Aryl Bromides (pages 13619–13623)

      Dr. Xiao-Feng Wu, Dr. Helfried Neumann, Stephan Neumann and Prof. Dr. Matthias Beller

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/chem.201202652

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      Oxazoline is OK! A general and efficient method for the synthesis of oxazolines has been developed (see scheme). This allowed the preparation of 27 five-membered-ring heterocycles and 11 six-membered-ring heterocycles in moderate to good yields.

    10. Asymmetric Catalysis

      Toward Efficient Asymmetric Carbon–Carbon Bond Formation: Continuous Flow with Chiral Heterogeneous Catalysts (pages 13624–13628)

      Dr. Tetsu Tsubogo, Dr. Yasuhiro Yamashita and Prof. Dr. Shū Kobayashi

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/chem.201202896

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      A chiral Ca catalyst based on CaCl2 with a chiral ligand was developed and applied to the asymmetric 1,4-addition of 1,3-dicarbonyl compounds to nitroalkenes as a model system. To address product inhibition issues, the Ca catalyst was applied to continuous flow with a chiral heterogeneous catalyst. The continuous flow system using a newly synthesized, polymer-supported Pybox was successfully employed, and the TON was improved 25-fold compared with those of the previous Ca(OR)2 catalysts.

    11. Fluorescent Probes

      Single Fluorescent Probe Displays a Distinct Response to Zn2+ and Cd2+ (pages 13629–13632)

      Jiaoliang Wang, Prof. Weiying Lin and Weiling Li

      Version of Record online: 13 SEP 2012 | DOI: 10.1002/chem.201202146

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      Single probe, multiple targets: The design and synthesis of a new probe is described that can readily discriminate Zn2+ and Cd2+ with different fluorescence signals (see figure). The studies of Job's plot, mass spectroscopy, DFT calculations, and 1H NMR spectroscopy reveal that the new probe has possible distinct binding modes to Zn2+ and Cd2+. This work may open up new opportunities for the development of single fluorescent probes that can sense multiple targets of interest.

    12. Gas-Phase Reactions

      Determination of Intrinsic Binding Modes by Mass Spectrometry: Gas-Phase Behavior of Adamantylated Bisimidazolium Guests Complexed to Cucurbiturils (pages 13633–13637)

      Jarmila Černochová, Petra Branná, Dr. Michal Rouchal, Dr. Petr Kulhánek, Dr. Ivo Kuřitka and Dr. Robert Vícha

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/chem.201201444

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      Adamantylated bisimidazolium cations exhibit a distinct fragmentation pathway in contrast to their cucurbit[7]uril (CB7) complexes (see scheme). The observed alternative fragmentation of the guest molecule in a complex clearly correlates to the supposed sterically hindered or allowed slippage of the macrocycle over the axel molecule.

    13. Gold Catalysis

      Gold-Catalyzed Cyclization–Cycloaddition Cascade Reactions of Allenyl Acetals with Nitrones (pages 13638–13641)

      Dr. Dhananjayan Vasu and Prof. Dr. Rai-Shung Liu

      Version of Record online: 17 SEP 2012 | DOI: 10.1002/chem.201201777

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      Gold and silver: When allenyl acetals and nitrones are treated with a catalytic amount of a gold complex and a silver salt they react through a cyclization—cycloaddition cascade reaction to give a mixture of diastereomeric tricyclic products. The mixture converges to a single product upon acid hydrolysis (see scheme). The key intermediate is postulated to be a 1-methoxyfulvene species.

  6. Full Papers

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

      One-Step Hydrothermal Synthesis of Carboxyl-Functionalized Upconversion Phosphors for Bioapplications (pages 13642–13650)

      Jianping Yang, Dr. Dengke Shen, Xiaomin Li, Wei Li, Yin Fang, Yong Wei, Chi Yao, Prof. Bo Tu, Prof. Fan Zhang and Prof. Dongyuan Zhao

      Version of Record online: 20 SEP 2012 | DOI: 10.1002/chem.201202336

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      One step at a time: Carboxyl-functionalized upconversion phosphors have been successfully synthesized with a facile one-step hydrothermal approach by using a small-molecule binary acid as capping agent (see figure). This is an environmental friendly and facile approach to the large-scale synthesis of carboxyl-functionalized upconversion materials with controlled phases, shapes, and sizes.

    2. Electron Transfer

      Nondestructive Photoluminescence Read-Out by Intramolecular Electron Transfer in a Perylene Bisimide-Diarylethene Dyad (pages 13651–13664)

      Martin Berberich, Mirco Natali, Peter Spenst, Dr. Claudio Chiorboli, Prof. Dr. Franco Scandola and Prof. Dr. Frank Würthner

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/chem.201201484

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      Tuning fluorescence: A novel, highly stable, photochromic dyad based on a perylene bisimide fluorophore and a diarylethene photochrome was synthesized and its optical and photophysical properties were studied in detail by steady-state and time-resolved ultrafast spectroscopy (see figure; o=open form, c= closed form). Solvent-dependent fluorescence studies revealed that the emission of the ring-closed form is drastically quenched in solvents of medium-to-high polarities.

    3. Perylene Bisimides

      Perylene Bisimide Dimer Aggregates: Fundamental Insights into Self-Assembly by NMR and UV/Vis Spectroscopy (pages 13665–13677)

      Changzhun Shao, Dr. Matthias Grüne, Dr. Matthias Stolte and Prof. Dr. Frank Würthner

      Version of Record online: 23 SEP 2012 | DOI: 10.1002/chem.201201661

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      Self-assembly control: Proper steric control can program the formation of well-defined perylene bisimide (PBI) dimer aggregates (see figure) in chloroform (“good” solvent). The further growth of PBIs into extended aggregates can be triggered by the addition of methylcyclohexane (“bad” solvent). These processes have been investigated in great detail and may serve as a guideline for an in-depth characterization of dye aggregates.

    4. Dendrimers

      Dendrimer Functionalization with a Membrane-Interacting Domain of Herpes Simplex Virus Type 1: Towards Intracellular Delivery (pages 13678–13685)

      Tom P. Carberry, Rossella Tarallo, Dr. Annarita Falanga, Dr. Emiliana Finamore, Prof. Dr. Massimiliano Galdiero, Prof. Dr. Marcus Weck and Prof. Dr. Stefania Galdiero

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/chem.201202358

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      Break on through: A dendrimer was functionalized with the membrane-interacting peptide gH(625–644) derived from the herpes simplex virus type 1 glycoprotein H, which is known to interact with the cellular membrane. Attachment of gH625 allowed the conjugate to penetrate into the cellular matrix mainly by a passive translocation mechanism. This peptidodendrimeric scaffold may be a useful delivery vehicle for therapeutics.

    5. Host–Guest Systems

      7,7′-Diamino-2,2′-diindolylmethane: A Building Block for Highly Efficient and Selective Anion Receptors—Studies in Solution and in the Solid State (pages 13686–13701)

      Paweł Dydio, Dawid Lichosyt, Dr. Tomasz Zieliński and Prof. Janusz Jurczak

      Version of Record online: 13 SEP 2012 | DOI: 10.1002/chem.201201909

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      One to catch them all! A series of amide and urea derivatives of 7,7′-diamino-2,2′-diindolylmethane (DIM) that can recognise various anions through hydrogen bonding, even in very demanding solvents (DMSO/water, methanol), has been prepared. The efficiency and selectivity of these receptors depends on the side groups introduced and their conformational preferences. The binding mode for different anions is demonstrated by X-ray crystallography (see figure).

    6. Nanostructures

      Ultrathin Ca-PO4-CO3 Solid-Solution Nanowires: A Controllable Synthesis and Full-Color Emission by Rare-Earth Doping (pages 13702–13711)

      Dr. Junfeng Hui, Dr. Qiyu Yu, Dr. Yong Long, Dr. Zhicheng Zhang, Dr. Yong Yang, Dr. Pengpeng Wang, Dr. Biao Xu and Prof. Dr. Xun Wang

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/chem.201201277

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      Totally wired: A series of ultrathin Ca-PO4-CO3 solid-solution nanowires with sizes and morphologies that can be tuned by changing the PO43−/CO32− ratio were prepared by a simple hydrothermal process. Some of the as-prepared ultrathin nanowires showed bright blue luminescence, and doping with Tb3+ or Eu3+ ions resulted in bright red or green fluorescence. Additive color mixtures of these primary colors reproduced a full color range (see figure).

    7. Self-Assembly

      Sterically-Limited Self-Assembly of Pt4 Macrocycles into Discrete Non-covalent Nanotubes: Porous Supramolecular Tetramers and Hexamers (pages 13712–13721)

      Dr. Peter D. Frischmann, Brian J. Sahli, Dr. Samuel Guieu, Dr. Brian O. Patrick and Prof. Mark J. MacLachlan

      Version of Record online: 20 SEP 2012 | DOI: 10.1002/chem.201201536

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      Stacked to the max: Sterically demanding substituents limit the columnar organization of metallomacrocycles into discrete hexamers and tetramers (see figure). By limiting one-dimensional macrocycle aggregation to finite non-covalent nanotubes, significant molecular porosity is engineered into the materials. The concepts presented here for isolating discrete aggregates may be generalized to other one-dimensional assembling systems.

    8. Supramolecular Chemistry

      Effects of Axle-Core, Macrocycle, and Side-Station Structures on the Threading and Hydrolysis Processes of Imine-Bridged Rotaxanes (pages 13722–13732)

      Hiroyoshi Sugino, Prof. Hidetoshi Kawai, Dr. Takeshi Umehara, Prof. Kenshu Fujiwara and Prof. Takanori Suzuki

      Version of Record online: 20 SEP 2012 | DOI: 10.1002/chem.201200837

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      Threading macrocycles: Variation of the imine-bridging station, side-station, and/or macrocycle structures all affect the threading process of the axle in the macrocycle and the hydrolysis generating nonbridged [2]rotaxane (see scheme).

    9. Combinatorial Chemistry

      You have full text access to this OnlineOpen article
      The Use of Electrospray Mass Spectrometry to Determine Speciation in a Dynamic Combinatorial Library for Anion Recognition (pages 13733–13742)

      Dr. Hazel I. A. Phillips, Dr. Aleksey V. Chernikov, Dr. Nicholas C. Fletcher, Prof. Dr. Alison E. Ashcroft, Dr. James R. Ault, Dr. Maria H. Filby and Dr. Andrew J. Wilson

      Version of Record online: 20 SEP 2012 | DOI: 10.1002/chem.201201302

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      Dynamic anion recognition: The use of a dynamic library of bipyridine ligands in the presence of iron(II) has been investigated by electrospray mass spectrometry, allowing good speciation of the dominant complexes to be observed (see figure). This has been used to determine a change in the observed equilibrium with the introduction of chloride; the system is able to self-select the ideal ligand combination to permit anion recognition.

    10. Polyoxometalates

      Controlling the Self-Assembly of a Mixed-Metal Mo/V–Selenite Family of Polyoxometalates (pages 13743–13754)

      M. Nieves Corella-Ochoa, Dr. Haralampos N. Miras, Dr. De-Liang Long and Prof. Leroy Cronin

      Version of Record online: 20 SEP 2012 | DOI: 10.1002/chem.201200912

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      Design it! A novel family of the largest mixed-metal Mo/V–selenite polyoxometalates (POMs) has been synthesised by controlling the interplaybetween the pyramidal SeO32− inorganic ligand, the cations and the Mo/V-based building blocks and by directing their self-assembly towards the formation of unprecedented high-nuclearity architectures. The discovery of novel coordination modes of the SeO32− demonstrates the potential for further design of novel POM-based materials (see figure).

    11. Nanocomposites

      Reactive Polymer as a Versatile Toolbox for Construction of Multifunctional Superparamagnetic Nanocomposites (pages 13755–13761)

      Ying Shen , Lingzhi Zhao , Prof. Li Qi, Dr. Juan Qiao, Prof. Lanqun Mao and Prof. Yi Chen

      Version of Record online: 17 SEP 2012 | DOI: 10.1002/chem.201201993

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      A versatile platform for construction of magnetic nanocomposites for cell imaging has been developed by using poly(glycidyl methacrylate) as a reactive polymer to combine with a fluorescent dye and the surface of Fe3O4 magnetic nanoparticles. After conjugation with transferrin, which specifically targets cells overexpressing transferrin receptors, the nanocomposites could be used to selectively recognize Hela cells (see figure).

    12. Mesoporous Materials

      Spiky Mesoporous Anatase Titania Beads: A Metastable Ammonium Titanate-Mediated Synthesis (pages 13762–13769)

      Dr. Dehong Chen, Dr. Fuzhi Huang, Lu Cao, Prof. Yi-Bing Cheng and Prof. Rachel A. Caruso

      Version of Record online: 27 SEP 2012 | DOI: 10.1002/chem.201202539

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      A sharp synthesis: Monodisperse spiky mesoporous anatase titania beads were fabricated through a controllable phase transformation and crystallization process from amorphous precursor beads to metastable amorphous titania/ammonium titanate core-shell structures, and finally to anatase titania beads (see figure). The resulting beads show potential as working electrodes for high-performance dye-sensitized solar cells.

    13. NMR spectroscopy

      Solid-State 73Ge NMR Spectroscopy of Simple Organogermanes (pages 13770–13779)

      Margaret A. Hanson, Andre Sutrisno, Victor V. Terskikh, Kim M. Baines and Yining Huang

      Version of Record online: 28 SEP 2012 | DOI: 10.1002/chem.201201944

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      Solid-state 73Ge NMR: Spectra of several simple organogermanium compounds are reported. NMR parameters are related to structural metrics and used in combination with DFT calculations to propose potential structures of several compounds without known crystals structures. It is possible to obtain high-quality spectra even for a challenging nucleus (see figure).

    14. Asymmetric Synthesis

      Asymmetric Hydrogenation of α,β-Unsaturated Carboxylic Esters with Chiral Iridium N,P Ligand Complexes (pages 13780–13786)

      Dr. David H. Woodmansee, Marc-André Müller, Dr. Lars Tröndlin, Esther Hörmann and Prof. Andreas Pfaltz

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/chem.201202397

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      Enantioselective conjugate reduction of a wide range of α,β-unsaturated carboxylic esters was achieved using chiral Ir N,P complexes as hydrogenation catalysts. The resulting saturated esters with a stereogenic center in the α or β position were obtained in high enantiomeric purity (see scheme).

    15. Platinum Chemistry

      Supramolecular Assembly of Diplatinum Species through Weak PtII⋅⋅⋅PtII Intermolecular Interactions: A Combined Experimental and Computational Study (pages 13787–13799)

      Dr. Alejandro Pérez Paz, Leonardo A. Espinosa Leal, Mohammad-Reza Azani, Dr. Alejandro Guijarro, Dr. Pablo J. Sanz Miguel, Gonzalo Givaja, Dr. Oscar Castillo, Dr. Rubén Mas-Ballesté, Dr. Félix Zamora and Prof. Angel Rubio

      Version of Record online: 14 SEP 2012 | DOI: 10.1002/chem.201201962

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      Line dancing in diplatinum compounds: The effect of temperature, concentration, solvent and the nature of the ligand L in the association of [Pt2L4] compounds, which can be followed by UV/Vis spectroscopy (see figure), were studied. Computational simulations show that the broad band at 760 nm appearing at low temperatures and high concentrations is due to the formation of [Pt2L4]n supramolecules assembled through weak intermolecular Pt⋅⋅⋅Pt interactions.

    16. Self-Assembly

      Graphene Nanosheets as a Platform for the 2D Ordering of Metal Oxide Nanoparticles: Mesoporous 2D Aggregate of Anatase TiO2 Nanoparticles with Improved Electrode Performance (pages 13800–13809)

      Jang Mee Lee, In Young Kim, Song Yi Han, Tae Woo Kim and Prof. Seong-Ju Hwang

      Version of Record online: 17 SEP 2012 | DOI: 10.1002/chem.201200551

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      Between the sheets: A mesoporous 2D aggregate of TiO2 nanoparticles was successfully synthesized by the application of reduced graphene oxide (RGO) as a platform for particle ordering (see figure). The resulting assembled TiO2 nanoparticles exhibit promising electrode performances with low charge-transfer resistance.

    17. Ring Expansion

      Preparation of Stable Low-Oxidation-State Group 14 Element Amidohydrides and Hydride-Mediated Ring-Expansion Chemistry of N-Heterocyclic Carbenes (pages 13810–13820)

      S. M. Ibrahim Al-Rafia, Dr. Robert McDonald, Dr. Michael J. Ferguson and Prof. Dr. Eric Rivard

      Version of Record online: 17 SEP 2012 | DOI: 10.1002/chem.201202195

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      Breaking the ring that binds: A series of low-oxidation-state Group 14 element hydridoamides, NHCEH(BH3)NHDipp (E=Si or Ge; NHC=N-heterocyclic carbene; Dipp=2,6-iPr2C6H3), is reported. These hydrides underwent transmetallation upon heating to give IPrH2BNHDipp; this borane participates in C[BOND]N bond-activation reactions involving a carbene donor at 100 °C.

    18. Heterocyclic Chemistry

      Sterically Hindered o-Quinone Annulated with Dithiete: A Molecule Comprising Diolate and Dithiolate Coordination Sites (pages 13821–13827)

      Prof. Vladimir K. Cherkasov, Prof. Gleb A. Abakumov, Dr. Georgy K. Fukin, Dr. Svetlana V. Klementyeva and Dr. Viacheslav A. Kuropatov

      Version of Record online: 17 SEP 2012 | DOI: 10.1002/chem.201202343

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      Two-faced: A stable 1,2-benzodithiete annulated to o-quinone has been obtained by the alkaline hydrolysis of a 1,3-dithiol-2-one derivative followed by oxidation of the intermediate species (see scheme). The dithiete function is protected by bulky tert-butyl groups. Both coordination sites of this species are suitable for coordination of the metal. The ability of diolate and dithiolate “faces” to bind metals has also been studied.

    19. Electroluminescence

      Nondoped Deep-Blue Organic Light-Emitting Diodes with Color Stability and Very Low Efficiency Roll-Off: Solution-Processable Small-Molecule Fluorophores by Phosphine Oxide Linkage (pages 13828–13835)

      Cui Liu, Yu Gu, Qiang Fu, Ning Sun, Cheng Zhong, Prof. Dongge Ma, Prof. Jingui Qin and Prof. Chuluo Yang

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/chem.201201512

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      Deep-blue small-molecule fluorescent emitters with solution processsability were designed and synthesized by linking N-phenylnaphthalen-1-amine groups to a phenyl phosphine oxide core through a π-conjugated bridge. Solution-processed small-molecule-based organic light-emitting diodes featuring PO4 as emitter (see figure) achieve a maximum current efficiency of 2.36 cd A−1 with CIE coordinates of (0.15, 0.11).

    20. Chiral Macrocycles

      Rotation-Locked 2,6-Pyrido-allenophanes: Characterization of all Stereoisomers (pages 13836–13843)

      Inmaculada R. Lahoz, Dr. Armando Navarro-Vázquez, Dr. Antonio L. Llamas-Saiz, Dr. José Lorenzo Alonso-Gómez and Prof. M. Magdalena Cid

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/chem.201201186

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      Chiral macrocycles: New 2,6-disubstituted pyrido-allenophanes were designed, synthesized, and fully characterized thanks to the interplay between NMR, circular dichroism, X-ray diffraction, and theoretical calculations (see figure). The encapsulation of two molecules of chloroform by one of the isomers highlights their potential use as molecular hosts.

    21. Artificial Photosynthesis

      Ultrafast Photoinduced Energy and Electron Transfer in Multi-Modular Donor–Acceptor Conjugates (pages 13844–13853)

      Dr. Mohamed E. El-Khouly, Dr. Channa A. Wijesinghe, Dr. Vladimir N. Nesterov, Prof. Melvin E. Zandler, Prof. Shunichi Fukuzumi and Prof. Francis D'Souza

      Version of Record online: 20 SEP 2012 | DOI: 10.1002/chem.201202265

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      Multi-modular polyads featuring both energy-harvesting and electron-transferring entities are assembled by using both covalent and non-covalent methods. Ultrafast energy-transfer is observed in the triphenylamine–boron dipyrrin–zinc porphyrin triad (see scheme). Efficient charge separation leading to the generation of radical ion-pair species is observed in the triads, signifying their importance as materials for light energy-harvesting applications.

    22. Zeolites

      A Thorough Investigation of the Active Titanium Species in TS-1 Zeolite by In Situ UV Resonance Raman Spectroscopy (pages 13854–13860)

      Qiang Guo, Dr. Keju Sun, Prof. Dr. Zhaochi Feng, Dr. Guanna Li, Meiling Guo, Dr. Fengtao Fan and Prof. Dr. Can Li

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/chem.201201319

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      Ac-Ti-ve: A new kind of active titanium species in TS-1 zeolite, in addition to the tetrahedrally coordinated Ti sites, was identified with a resonance Raman band at 695 cm−1 at 266 nm excitation (see figure). These species showed high activities for epoxidation reactions. In situ UV resonance Raman spectroscopic studies revealed the catalytic reaction pathways.

    23. Alkaloids

      Asymmetric Total Synthesis of (−)-Stenine and 9a-epi-Stenine (pages 13861–13870)

      Prof. Dr. Hiromichi Fujioka, Kenji Nakahara, Naoyuki Kotoku, Yusuke Ohba, Yasushi Nagatomi, Tsung-Lung Wang, Yoshinari Sawama, Kenichi Murai, Kie Hirano, Tomohiro Oki, Shintaro Wakamatsu and Prof. Dr. Yasuyuki Kita

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/chem.201200376

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      Stereocontrolled synthesis: Stereocontrolled syntheses of (−)-stenine and 9a-epi-stenine have been developed by using a common cyclohexenone intermediate (see scheme). All six stereogenic centers in the cyclohexane ring were introduced with a high degree of stereoselectivity.

    24. DNA

      A Competitive Strategy Coupled with Endonuclease-Assisted Target Recycling for DNA Detection Using Silver-Nanoparticle-Tagged Carbon Nanospheres as Labels (pages 13871–13876)

      Zhu Zhu, Fenglei Gao, Dr. Jianping Lei, Dr. Haifeng Dong and Prof. Huangxian Ju

      Version of Record online: 17 SEP 2012 | DOI: 10.1002/chem.201201307

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      Sense-ational: A competitive strategy was designed for ultrasensitive detection of sequence-specific DNA by combining homogeneous endonuclease-assisted target DNA recycling with streptavidin-functionalized silver-nanoparticle-tagged carbon nanospheres as electrochemical labels (see figure). The sensing strategy showed excellent performance.

    25. Graphene

      Effects of Heat Treatment on Raman Spectra of Two-Layer 12C/13C Graphene (pages 13877–13884)

      Dr. Martin Kalbac, Otakar Frank and Prof. Ladislav Kavan

      Version of Record online: 13 SEP 2012 | DOI: 10.1002/chem.201202114

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      High is low: By using isotopic labeling it was demonstrated that the top layer in two-layer graphene exhibits much lower Raman temperature coefficients than the bottom one for both the G and the G′ modes (see figure).

    26. Transfer Hydrogenation

      Metal Amidoboranes: Superior Double-Hydrogen-Transfer Agents in the Reduction of Ketones and Imines (pages 13885–13892)

      Weiliang Xu, Prof. Dr. Guotao Wu, Wei Yao, Prof. Dr. Hongjun Fan, Jishan Wu and Prof. Dr. Ping Chen

      Version of Record online: 18 SEP 2012 | DOI: 10.1002/chem.201201301

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      Metal amidoboranes (MABs), such as lithium amidoborane, sodium amidoborane, and calcium amidoborane, reduce ketones and imines into their corresponding secondary alcohols and amines, respectively, at room temperature with high conversion and yields.

  7. Corrigendum

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    8. Corrigendum
    1. You have free access to this content
      Corrigendum: A General Synthesis of Alkenyl-Substituted Benzofurans, Indoles, and Isoquinolones by Cascade Palladium-Catalyzed Heterocyclization/Oxidative Heck Coupling (pages 13894–13896)

      Dr. Rosana Álvarez, Claudio Martínez, Youssef Madich, J. Gabriel Denis, Dr. José M. Aurrecoechea and Prof. Ángel R. de Lera

      Version of Record online: 19 SEP 2012 | DOI: 10.1002/chem.201201973

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