Chemistry - A European Journal

Cover image for Vol. 19 Issue 31

July 29, 2013

Volume 19, Issue 31

Pages 10061–10418

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Full Papers
    1. You have free access to this content
      Cover Picture: Histone-Deacetylase-Targeted Fluorescent Ruthenium(II) Polypyridyl Complexes as Potent Anticancer Agents (Chem. Eur. J. 31/2013) (page 10061)

      Rui-Rong Ye, Dr. Zhuo-Feng Ke, Dr. Cai-Ping Tan, Liang He, Prof. Liang-Nian Ji and Prof. Dr. Zong-Wan Mao

      Article first published online: 19 JUL 2013 | DOI: 10.1002/chem.201390113

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      Fluorescent ruthenium complexes have been used as inhibitors of histone deacetylases (HDACs). In their Full Paper on page 10160 ff., Z.-W Mao, C.-P. Tan, and co-workers report a series of red fluorescent ruthenium(II) complexes that can inhibit HDAC and induce apoptotic cell death in tumor cells. These fluorescent RuII-HDACi conjugates represent a promising class of anticancer agents for potential dual imaging and therapeutic applications targeting HDACs (cover graphic by Mu-Qiang Wei).

    2. You have free access to this content
      Back Cover: Encapsulation of Metalloporphyrins in a Self-Assembled Cubic M8L6 Cage: A New Molecular Flask for Cobalt–Porphyrin-Catalysed Radical-Type Reactions (Chem. Eur. J. 31/2013) (page 10420)

      Dr. Matthias Otte, Petrus F. Kuijpers, Dipl.-Chem. Oliver Troeppner, Prof. Dr. Ivana Ivanović-Burmazović, Prof. Dr. Joost N. H. Reek and Prof. Dr. Bas de Bruin

      Article first published online: 19 JUL 2013 | DOI: 10.1002/chem.201390116

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      Radicals caged in a cube! A new, large cubic M8L6 host capable of encapsulating a catalytically active metalloradical-type cobalt–porphyrin catalyst is described by de Bruin and co-workers in their Full Paper on page 10170 ff. The reactions mediated by this system are the first examples of cobalt–porphyrin-catalyzed radical-type transformations involving diazo compounds that occur inside a supramolecular cage. The cover is an artistic impression of their work in the typical cubistic style of the Dutch painter Piet Mondriaan.

  2. Graphical Abstract

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

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Full Papers
    1. Kinetics

      Mechanism of Palladium-Catalyzed Suzuki–Miyaura Reactions: Multiple and Antagonistic Roles of Anionic “Bases” and Their Countercations (pages 10082–10093)

      Dr. Christian Amatore, Dr. Gaëtan Le Duc and Dr. Anny Jutand

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300177

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      One base, four roles: In Suzuki–Miyaura reactions, anionic bases OH and F play multiple antagonistic roles (see scheme). Two are positive: formation of reactive [Pd(Ar)(L)2(OH)] or [Pd(Ar)F(L)2] (L=PPh3) and catalysis of the reductive elimination from trans-[Pd(Ar)(Ar′)(L)2]. Two are negative: formation of unreactive arylborates or fluoroborates and complexation of the OH group of [Pd(Ar)(L)2(OH)] by the countercation of the base.

  5. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Full Papers
    1. Metallocycles

      Stimuli-Responsive Supramolecular Gels through Hierarchical Self-Assembly of Discrete Rhomboidal Metallacycles (pages 10094–10100)

      Guang-Zhen Zhao, Li-Jun Chen, Wei Wang, Jing Zhang, Guang Yang, De-Xian Wang, Yihua Yu and Hai-Bo Yang

      Article first published online: 10 JUL 2013 | DOI: 10.1002/chem.201301385

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      A new class of supramolecular organometallic gels with a discrete rhomboidal metallacycle as the main skeleton was fabricated through hierarchical self-assembly (see figure). More importantly, by taking advantage of the dynamic nature of metal–ligand bonds, the stimuli-responsive gel–sol transition of the obtained gels was realized by disassembly and reassembly of the rhomboidal scaffold as controlled by bromide anions.

      Corrected by:

      Corrigendum: Corrigendum: Stimuli-Responsive Supramolecular Gels through Hierarchical Self-Assembly of Discrete Rhomboidal Metallacycles

      Vol. 19, Issue 39, 12923, Article first published online: 19 SEP 2013

    2. Bioinorganic Chemistry

      A Functional Model for the Rieske Center: Full Characterization of a Biomimetic N-Ligated [2Fe-2S] Cluster in Different Protonation States (pages 10101–10106)

      Antonia Albers, Thomas Bayer, Dr. Serhiy Demeshko, Dr. Sebastian Dechert and Prof. Dr. Franc Meyer

      Article first published online: 18 JUN 2013 | DOI: 10.1002/chem.201301760

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      Give and take both: A bis(benzimidazolate)-capped biomimetic [2Fe-2S] cluster has been characterized in different protonation states, both in the diferric and mixed-valent forms. Protonation does not lead to structural changes of the [2Fe-2S] core, but facilitates its reduction and causes pronounced valence localization in the mixed-valent state. Concerted proton and electron transfer back to the diferric cluster emulates a key step in the function of mitochondrial Rieske proteins (see scheme).

    3. Electrochemistry

      Enhanced Performance of Dye-Sensitized Solar Cells Using Solution-Based In Situ Synthesis and Fabrication of Cu2ZnSnSe4 Nanocrystal Counter Electrode (pages 10107–10110)

      Sheng-Jie Yuan, Dr. Zheng-Ji Zhou, Ze-Liang Hou, Dr. Wen-Hui Zhou, Rong-Yue Yao, Yang Zhao and Prof. Dr. Si-Xin Wu

      Article first published online: 18 JUN 2013 | DOI: 10.1002/chem.201300283

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      On the bright side: A solution-based strategy was developed for in situ synthesis and film deposition of Cu2ZnSnSe4 nanocrystal films (samples a–d). The obtained Cu2ZnSnSe4 nanocrystal films can be used as an effective counter-electrode (CE) material to replace Pt, and yield low-cost, high-efficiency dye-sensitized solar cells (DSSCs). The assembled solar cell devices exhibit an efficiency of 7.82 % under 1 sun irradiation (see figure).

    4. Metal Etching

      Effective One-Step Gold Dissolution Using Environmentally Friendly Low-Cost Reagents (pages 10111–10114)

      Dr. Angela Serpe, Dr. Luciano Marchiò, Dr. Flavia Artizzu, Prof. M. Laura Mercuri and Prof. Paola Deplano

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300940

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      Digging for gold: Mixtures of tetraethylthiuram disulfide (Et4TDS) and I2 in acetone are capable of dissolving elemental gold and forming valuable metal complexes, in which the stoichiometry depends on the mixture composition. These mixtures can also etch the gold layer homogeneously and selectively from Si/SiO2/Ti/Au thin-layered structures under mild conditions (see figure).

    5. Chemical Sensors

      A Highly Sensitive Fluorescent Chemosensor for Ruthenium: Oxidation Plays a Triple Role (pages 10115–10118)

      Bo Chen, Prof. Fengling Song, Dr. Shiguo Sun, Dr. Jiangli Fan and Prof. Xiaojun Peng

      Article first published online: 13 JUN 2013 | DOI: 10.1002/chem.201300951

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      Ruthenium comes to its senses: Determining how effectively ruthenium residues are removed from olefin metathesis reactions calls for an alternative evaluation method to ICP-MS. A fluorescent chemosensor for ruthenium has been developed based on an alkene oxidation reaction (see figure). This fluorescence method has a good selectivity as well as an excellent sensitivity and a 0.32 ppb detection limit. Its streamlined and high-throughput character is demonstrated by sensing residual Ru in samples containing functionalized organic compounds.

    6. Aromatic Polycycles

      From Simple Furans to Complex Nitrogen-Bearing Aromatic Polycycles by Means of a Flexible and General Reaction Sequence Initiated by Singlet Oxygen (pages 10119–10123)

      Dr. Dimitris Kalaitzakis, Dr. Tamsyn Montagnon, Eirini Antonatou, Nuria Bardají and Prof. Dr. Georgios Vassilikogiannakis

      Article first published online: 14 JUN 2013 | DOI: 10.1002/chem.201301571

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      All-in-one: A new and general one-pot reaction sequence initiated by singlet oxygen that transforms simple furan substrates into complex nitrogen-bearing aromatic polycycles having all the structural features of a number of important natural products (for example, the erythrina alkaloids; see scheme, RB=rose Bengal) is reported. The reaction sequence itself uses mild conditions and has wide functional group tolerance.

    7. C[BOND]H Activation

      Cobalt-Catalyzed Hydrosilation/Hydrogen-Transfer Cascade Reaction: A New Route to Silyl Enol Ethers (pages 10124–10127)

      Dr. Thomas W. Lyons and Prof. Maurice Brookhart

      Article first published online: 18 JUN 2013 | DOI: 10.1002/chem.201301502

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      Capitalizing on cobalt: A new route to silyl enol ethers employing a Co-catalyzed cascade reaction featuring a tandem hydrosilation/hydrogen-transfer reaction is reported. The low catalyst loading, mild reaction conditions, and unique η2-silane resting state showcase the impressive utility of this seldom used transition-metal catalyst in C[BOND]H activation reactions (see scheme; VTMS = vinyltrimethylsilane; Cp* = 1,2,3,4,5-pentamethylcyclopentadiene).

    8. Tautomerization

      Experimental Evidences in Favour of the Hydroxylamine[RIGHTWARDS ARROW]Nitrene–Water Tautomerization on the Coordination Sphere of IrIII Centres (pages 10128–10131)

      Crispín Cristóbal, Dr. Joaquín López-Serrano, Dr. Ana M. Lozano-Vila, Prof. Dr. Margarita Paneque, Prof. Dr. Manuel L. Poveda, Florencia Vattier, Ángela Vivancos and Dr. Eleuterio Álvarez

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300624

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      And, to round off … A series of IrIII 5-membered metallacycles with an Ir[BOND]CH2 bond, react with aq. NH2OH with formation of hydride 6-membered iridacyclic complexes, which contain an Ir[BOND]NH[DOUBLE BOND]CH[BOND] imine functionality (see scheme).

    9. Cascade Reactions

      A Cascade Coupling Strategy for One-Pot Total Synthesis of β-Carboline and Isoquinoline-Containing Natural Products and Derivatives (pages 10132–10137)

      Dr. Yan-Ping Zhu, Mei-Cai Liu, Qun Cai, Feng-Cheng Jia and Prof. An-Xin Wu

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201301734

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      Multi-birds with one stone: A cascade coupling strategy was developed for the synthesis of β-carbolines. The method can direct the synthesis of β-carboline and isoquinoline-containing natural products with high yields. Moreover, this protocol can also be further applied towards the total synthesis of natural products fascaplysin and papaverin (see scheme).

    10. Cuprates

      First X-Ray Crystal Structure and Internal Reference Diffusion-Ordered NMR Spectroscopy Study of the Prototypical Posner Reagent, MeCu(SPh)Li(THF)3 (pages 10138–10141)

      Prof. Dr. Steven H. Bertz, Richard A. Hardin, Thomas J. Heavey, Prof. Dr. Daniel S. Jones, T. Blake Monroe, Dr. Michael D. Murphy, Prof. Dr. Craig A. Ogle and Tara N. Whaley

      Article first published online: 18 JUN 2013 | DOI: 10.1002/chem.201301415

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      Grow slow: The usual direct treatment of MeLi and CuSPh did not yield X-ray quality crystals of MeCu(SPh)Li. An indirect method starting from Me2CuLiLiSPh and chalcone afforded the desired crystals by the slow reaction of the intermediate π-complex (see scheme). This strategy produced the first X-ray crystal structure of a Posner cuprate. A complementary NMR study showed that the contact ion pair was also the main species in solution.

    11. Asymmetric Synthesis

      Highly Efficient Catalytic Enantioselective Mannich Reaction of Malonates with N-tert-Butoxycarbonyl Imines by Using Yb(OTf)3/Pybox Catalysts at Room Temperature (pages 10142–10145)

      Babak Karimi, Ehsan Jafari and Dieter Enders

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300241

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      Go Mannich! A highly efficient and enantioselective method for the direct asymmetric reaction of dibenzyl malonate with N-tert-butoxycarbonyl aldimines in the presence of Yb(OTf)3 and iPr-pybox complexes is described (see scheme; pybox=pyridine bisoxazoline).

    12. Gemini Surfactants

      An Efficient Route to Rapidly Access Silica Materials with Differently Ordered Mesostructures through Counteranion Exchange (pages 10146–10149)

      Changxu Lin, Wei Zhu, Jian Li, Xiyang Liu, Weina Li, Yin Jiang, Haowei Yang and Prof. Guangtao Li

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300597

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      Control via exchange: By using a new type of imidazolium-based gemini surfactant as the template, highly ordered cubic mesoporous silica material (MCM-48) was directly synthesized in a broad range of reactant compositions and under mild conditions (see scheme). Moreover, by a simple counterion exchange strategy, hexagonal (MCM-41) and lamellar (MCM-50) mesoporous silicas are also easily and efficiently accessible.

  6. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Full Papers
    1. Supramolecular Gels

      Fibrous Networks with Incorporated Macrocycles: A Chiral Stimuli-Responsive Supramolecular Supergelator and Its Application to Biocatalysis in Organic Media (pages 10150–10159)

      Zhenhui Qi, Dr. Changzhu Wu, Dr. Paula Malo de Molina, Han Sun, Andrea Schulz, Prof. Christian Griesinger, Prof. Michael Gradzielski, Prof. Rainer Haag, Prof. Marion B. Ansorge-Schumacher and Prof. Christoph A. Schalley

      Article first published online: 10 JUL 2013 | DOI: 10.1002/chem.201300193

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      Supramolecular gels: A versatile, crown ether substituted, chiral bis-urea gelator forms gels in a variety of organic solvents. The gel is sensitive to multiple chemical stimuli and the reversible sol–gel phase transitions can be triggered by host–guest interactions. The supramolecular gel can be used for enzyme immobilization and stimuli-induced release (see figure). When used in Pickering emulsions containing nanoparticle-stabilized gel microparticles with a polar inner phase, the gelator broadens the range of solvents in which enzymes can be used to catalyze reactions in nonpolar media.

    2. Enzyme Inhibition

      Histone-Deacetylase-Targeted Fluorescent Ruthenium(II) Polypyridyl Complexes as Potent Anticancer Agents (pages 10160–10169)

      Rui-Rong Ye, Dr. Zhuo-Feng Ke, Dr. Cai-Ping Tan, Liang He, Prof. Liang-Nian Ji and Prof. Dr. Zong-Wan Mao

      Article first published online: 4 JUL 2013 | DOI: 10.1002/chem.201300814

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      Bulky luminous hurdles: A series of fluorescent ruthenium(II) polypyridyl complexes targeting histone deacetylases (HDACs) as anticancer agents have been designed and synthesized. All of these complexes can inhibit HDAC activity. Mechanistic studies show that complex 1 (see figure) can induce apoptosis through mitochondrial dysfunction and the generation of reactive oxygen species.

    3. Catalysis

      Encapsulation of Metalloporphyrins in a Self-Assembled Cubic M8L6 Cage: A New Molecular Flask for Cobalt–Porphyrin-Catalysed Radical-Type Reactions (pages 10170–10178)

      Dr. Matthias Otte, Petrus F. Kuijpers, Dipl.-Chem. Oliver Troeppner, Prof. Dr. Ivana Ivanović-Burmazović, Prof. Dr. Joost N. H. Reek and Prof. Dr. Bas de Bruin

      Article first published online: 2 JUL 2013 | DOI: 10.1002/chem.201301411

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      Spirit of the cage: The encapsulation of a metalloporphyrin catalyst in a new M8L6 cage compound has been demonstrated (see structure). The catalyst inside the cubic cage catalyses radical-type reactions of diazo compounds.

    4. Fluorescent Probes

      You have full text access to this OnlineOpen article
      The Structural Basis for Optimal Performance of Oligothiophene-Based Fluorescent Amyloid Ligands: Conformational Flexibility is Essential for Spectral Assignment of a Diversity of Protein Aggregates (pages 10179–10192)

      Therése Klingstedt, Dr. Hamid Shirani, Dr. K. O. Andreas Åslund, Dr. Nigel J. Cairns, Dr. Christina J. Sigurdson, Prof. Michel Goedert and Dr. K. Peter R. Nilsson

      Article first published online: 18 JUN 2013 | DOI: 10.1002/chem.201301463

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      Freedom! Conformational freedom and extended conjugation of the conjugated backbone are important determinants for thiophene-based optical ligands for spectral assignment of disease-associated protein aggregates. Replacing the central thiophene ring with a phenyl moiety (see figure) abolished the spectral assignment of Aβ and tau aggregates as well as the detection of non-congophilic and non-thioflavinophilic protein aggregates.

    5. Lithium Storage

      Facile Microstructure Control of Mesoporous Co1.29Ni1.71O4 and the Effect of the Microstructure on Lithium-Storage Performance (pages 10193–10200)

      Ying Xiao, Changwen Hu and Prof. Minhua Cao

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300967

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      All shapes and sizes: Mesoporous Co1.29Ni1.71O4 microflowers, nanorods, and nanoparticles have been successfully designed and synthesized. The three samples all have a mesoporous structure but different pore-size distributions. The nanorod sample exhibits high capacity, good rate capability, and cycle stability as an anode material in lithium-ion batteries (see figure).

    6. Catalysts

      Ligand-Stabilized and Atomically Precise Gold Nanocluster Catalysis: A Case Study for Correlating Fundamental Electronic Properties with Catalysis (pages 10201–10208)

      Dr. Jing Liu, Dr. Katla Sai Krishna, Dr. Yaroslav B. Losovyj, Dr. Soma Chattopadhyay, Dr. Natalia Lozova, Prof. Jeffrey T. Miller, Prof. James J. Spivey and Dr. Challa S. S. R. Kumar

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300600

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      Precise clusters: Results from the investigation of correlating the styrene oxidation catalysis of atomically precise mixed-ligand biicosahedral-structure [Au25(PPh3)10(SC12H25)5Cl2]2+ and thiol-stabilized icosahedral core–shell-structure [Au25(SCH2CH2Ph)18] clusters with their electronic and atomic structure by using a combination of synchrotron-radiation-based X-ray absorption fine-structure spectroscopy (XAFS) and ultraviolet photoemission spectroscopy (UPS) are presented (see scheme).

    7. Europium Sensors

      Surface-Imprinted Nanofilaments for Europium-Amplified Luminescent Detection of Fluoroquinolone Antibiotics (pages 10209–10216)

      Jolanta Zdunek, Dr. Elena Benito-Peña, Dr. Ana Linares, Dr. Aude Falcimaigne-Cordin, Prof. Dr. Guillermo Orellana, Prof. Dr. Karsten Haupt and Prof. Dr. María C. Moreno-Bondi

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300101

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      Luminescent antibiotics! Surface-imprinted nanofilaments have been prepared by nanomolding in porous alumina by using enrofloxacin as the template (see figure). The sensing mechanism is based on the complexation of the selectively bound antimicrobial on the polymer film by europium(III) ions to yield a luminescent species showing long emission wavelengths, narrow emission bands, and large Stokes shifts, properties that are highly advantageous for sensing.

    8. Metal–Organic Frameworks

      Luminescent Metal–Organic Frameworks (MOFs) as a Chemopalette: Tuning the Thermochromic Behavior of Dual-Emissive Phosphorescence by Adjusting the Supramolecular Microenvironments (pages 10217–10225)

      Dr. Shun-Ze Zhan, Mian Li, Prof. Dr. Seik Weng Ng and Prof. Dr. Dan Li

      Article first published online: 18 JUN 2013 | DOI: 10.1002/chem.201204632

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      A colorful palette: A Cu4I4 and [Cu3Pz3]2 based metal–organic framework exhibits an intriguing chemopalette effect. The effect is regulated by the supramolecular microenvironment between the 2D layers of the metal–organic frameworks (see figure), in particular, by the Cu–Cu distances in the excimeric [Cu3(pyrazolate)3]2 luminophore. Control of the thermochromic behavior facilitates the understanding of these optical materials with unusual dual-emissive properties.

    9. Helical Structures

      Molecular Thermal Hysteresis in Helix-Dimer Formation of Sulfonamidohelicene Oligomers in Solution (pages 10226–10234)

      Dr. Masanori Shigeno, Yo Kushida and Prof. Dr. Masahiko Yamaguchi

      Article first published online: 14 JUN 2013 | DOI: 10.1002/chem.201204556

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      Know when to unfold 'em: Sulfonamidohelicene oligomers up to the nonamer level were synthesized. The tetramer formed a helix dimer in a fluorinated aromatic solvent, which unfolded with heating. This structural change exhibited molecular thermal hysteresis (see figure).

    10. Oxide Nanostructures

      On the Entangled Growth of NaTaO3 Cubes and Na2Ti3O7 Wires in Sodium Hydroxide Solution (pages 10235–10243)

      Dr. Stefan O. Baumann, Dr. Chang Liu, Dr. Michael J. Elser, Dr. Andreas Sternig, Dr. Nicolas Siedl, Dr. Thomas Berger and Prof. Dr. Oliver Diwald

      Article first published online: 18 JUN 2013 | DOI: 10.1002/chem.201204281

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      The die is cast: The entangled growth of Na2Ti3O7 nanowires and NaTaO3 cubes has been investigated by using different analytical methods and the influence of different titanium sources on the morphology of the resulting nanostructures was examined.

    11. Intermetallic Phases

      Pseudo-Fivefold Diffraction Symmetries in Tetrahedral Packing (pages 10244–10270)

      Prof. Stephen Lee, Dr. Ryan Henderson, Corey Kaminsky, Zachary Nelson, Jeffers Nguyen, Nick F. Settje, Dr. Joshua Teal Schmidt and Dr. Ji Feng

      Article first published online: 18 JUN 2013 | DOI: 10.1002/chem.201203758

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      Hidden symmetries: Metal crystal structures such as Cd3Cu4 (see figure) with its 1124 atom unit cell continue to intrigue. Why do such simple stoichiometries form such complex forms? Fivefold pseudosymmetries prove to be a unifying theme. In newly prepared Zn11Au15Cd23, the pseudosymmetries lead to an electron count that, to three significant figures, agrees with experiment.

    12. Self-Aggregation

      NMR Spectroscopic Study of the Self-Aggregation of 3-Hexen-1,5-diyne Derivatives (pages 10271–10279)

      Dr. Ana Pérez, Dr. Diana de Saá, Prof. Alfredo Ballesteros, Prof. José Luis Serrano, Dr. Teresa Sierra and Dr. Pilar Romero

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201204604

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      Come together: Polycatenar molecules derived from a highly conjugated rodlike core, that is, 1,6-diphenyl-3,4-dipropyl-3-hexen-1,5-diyne, self-aggregate. Analysis of the concentration- and temperature-dependent evolution of the chemical shifts of the NMR spectra of a solution of these molecules in [D12]cyclohexane show that the diffusion coefficients agree well with an isodesmic model of association in this solvent (see figure).

    13. Quantum Dots

      High-Performance Förster Resonance Energy Transfer (FRET)-Based Dye-Sensitized Solar Cells: Rational Design of Quantum Dots for Wide Solar-Spectrum Utilization (pages 10280–10286)

      Eunwoo Lee, Chanhoi Kim and Prof. Jyongsik Jang

      Article first published online: 13 JUN 2013 | DOI: 10.1002/chem.201300953

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      Live and FRET dye: High-performance FRET-based dye-sensitized solar cells have been successfully fabricated through the optimized design of a quantum-dot (QD) donor and a dye acceptor (D719) for simultaneous utilization of the wide solar spectrum with high conversion efficiency (see figure).

    14. Macrocyclic Ligands

      Oxo–Group-14-Element Bond Formation in Binuclear Uranium(V) Pacman Complexes (pages 10287–10294)

      Guy M. Jones, Prof. Polly L. Arnold and Dr. Jason B. Love

      Article first published online: 21 JUN 2013 | DOI: 10.1002/chem.201301067

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      Keeping it in the carbon family: Simple and versatile metalation and exchange reactions lead to a new family of binuclear uranium(V)–oxo complexes that are functionalised by the Group 14 elements C, Si, and Sn. These Pacman-shaped compounds display distinct U[BOND]O single and multiple bonding patterns and exhibit unique stability against oxidation (see scheme).

    15. Chiral Surfaces

      Chiral Thin Films of Metal Oxide (pages 10295–10301)

      Hagay Moshe, Maarten Vanbel, Dr. Ventsislav Kolev Valev, Prof. Thierry Verbiest, Dr. David Dressler and Prof. Yitzhak Mastai

      Article first published online: 21 JUN 2013 | DOI: 10.1002/chem.201300760

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      Layer upon layer: The synthesis of new chiral nanosized metal oxide surfaces based on chiral self-assembled monolayers (SAMs) coated with metal oxide (TiO2) nanolayers is described for the first time (see figure). This new type of nanosized chiral surface enables the protection of chiral self-assembled monolayers while preserving their enantioselective nature. The synthesis and characterization of these chiral surfaces are reported.

    16. Cage Compounds

      A New Approach to the Design of Neutral 10-C-5 Trigonal-Bipyramidal Carbon Compounds: A “π-Electron Cap” Effect (pages 10302–10311)

      Prof. Valery F. Sidorkin, Dr. Evgeniya P. Doronina and Dr. Elena F. Belogolova

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300461

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      Neutral 10-C-5 compounds are feasible! By using a revealed effect of steric compression of the 3c–4e axial XC1[LEFTWARDS ARROW]N fragment of the carbatranophanes (see figure), an increase in the coordination number of the carbon atom C1 of five was achieved (i.e., the optimization of the box size for C1 in the framework of the “ball-in-a-box” model).

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    17. Carbohydrates

      Sequential Norrish Type II Photoelimination and Intramolecular Aldol Cyclization of α-Diketones: Synthesis of Polyhydroxylated Cyclopentitols by Ring Contraction of Hexopyranose Carbohydrate Derivatives (pages 10312–10333)

      Dr. Dimitri Alvarez-Dorta, Dr. Elisa I. León, Dr. Alan R. Kennedy, Dr. Angeles Martín, Dr. Inés Pérez-Martín, Dr. Concepción Riesco-Fagundo and Prof. Dr. Ernesto Suárez

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201301230

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      Just light and heat! Visible-light photoexcitation of the innermost carbonyl of 2,3-diulose triggers an unprecedented Norrish type II photoelimination and uncatalyzed aldol sequential rearrangement through the thermal 5-(enol-exo)-exo-trig cyclization of the acyclic photoenol intermediate. The process involves a pyranosyl ring contraction and the formation of a new type of cyclopentitol derivatives with high diastereoselectivity (see scheme; R=acyl, alkyl, silyl group).

    18. Arylation

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      Arylation with Unsymmetrical Diaryliodonium Salts: A Chemoselectivity Study (pages 10334–10342)

      Joel Malmgren, Dr. Stefano Santoro, Dr. Nazli Jalalian, Prof. Fahmi Himo and Prof. Berit Olofsson

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300860

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      Salts with a choice: Phenols, anilines, and malonates were arylated under metal-free conditions with several aryl(phenyl)iodonium salts (see scheme). DFT calculations have been performed to investigate the reaction mechanism and elucidate the origins of the observed selectivities.

    19. Hydrogenation

      Ruthenium-Containing Phosphinesulfonate Chelate for the Hydrogenation of Aryl Ketones (pages 10343–10352)

      Fan Jiang, Kedong Yuan, Dr. Mathieu Achard and Dr. Christian Bruneau

      Article first published online: 21 JUN 2013 | DOI: 10.1002/chem.201301201

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      Laying down some RuIIs: Well-defined ruthenium(II) complexes that feature a phosphinesulfonate chelate were synthesized and efficiently applied in the hydrogenation of various aryl ketones.

    20. Arylation

      Peripheral Arylation of Subporphyrazines (pages 10353–10359)

      Tomohiro Higashino, Dr. M. Salomé Rodríguez-Morgade, Prof. Dr. Atsuhiro Osuka and Prof. Tomás Torres

      Article first published online: 19 JUN 2013 | DOI: 10.1002/chem.201301140

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      Conjugated cocoon: Peripherally hexaarylated subporphyrazines (SubPzs) have been prepared through a Pd-catalyzed, CuTC-mediated coupling of a hexaethylsulfanylated subporphyrazine with arylboronic acids. The introduced aryl substituents strongly influence the electronic properties of the subporphyrazine through effective conjugative interaction. The domed, extended π-system self-assembles in the solid state to form a dimeric capsule that houses a solvent molecule (see figure).

    21. Photoluminescence

      Luminescent Cyclometalated Alkynylplatinum(II) Complexes with a Tridentate Pyridine-Based N-Heterocyclic Carbene Ligand: Synthesis, Characterization, Electrochemistry, Photophysics, and Computational Studies (pages 10360–10369)

      Sammual Yu-Lut Leung, Elizabeth Suk-Hang Lam, Dr. Wai Han Lam, Dr. Keith Man-Chung Wong, Prof. Dr. Wing-Tak Wong and Prof. Dr. Vivian Wing-Wah Yam

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300493

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      Lighting up with platinum: The synthesis, characterization, electrochemistry, photophysics and computational studies of a new class of luminescent square-planar alkynylplatinum(II) complexes with a tridentate pyridine-based pincer-type N-heterocyclic carbene ligand, [Pt(C N C)(C[TRIPLE BOND]CR)][PF6] (C N C=2,6-bis(1-butylimidazol-2-ylidenyl)pyridine) have been reported (see figure).

    22. Nonlinear Optics

      Cyanine-Like Dyes with Large Bond-Length Alternation (pages 10370–10377)

      Dr. Karl J. Thorley, Dr. Joel M. Hales, Hyeongeu Kim, Dr. Shino Ohira, Prof. Jean-Luc Brédas, Prof. Joseph W. Perry and Prof. Harry L. Anderson

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300609

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      Like cyanines, yet different: New cationic dyes, which have alkyne bridges between the indole end groups, have been synthesized. Despite the large bond-length alternation (BLA), these carbocations display cyanine-like nonlinear optical behavior, such as large negative third-order hyperpolarizabilities, while exhibiting two-photon absorption behavior similar to that of triarylmethyl carbocations, such as brilliant green (see figure).

    23. C[BOND]H Activation

      Ruthenium-Catalyzed α-(Hetero)Arylation of Saturated Cyclic Amines: Reaction Scope and Mechanism (pages 10378–10387)

      Dr. Aldo Peschiulli, Veerle Smout, Dr. Thomas E. Storr, Dr. Emily A. Mitchell, Zdeněk Eliáš, Prof. Dr. Wouter Herrebout, Dr. Didier Berthelot, Dr. Lieven Meerpoel and Prof. Dr. Bert U. W. Maes

      Article first published online: 18 JUN 2013 | DOI: 10.1002/chem.201204438

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      Ring functionalization: Piperidines and structurally related saturated cyclic amines can be smoothly α-(hetero)arylated through direct sp3 C[BOND]H activation catalyzed by [Ru3(CO)12] (see scheme). Mechanistic studies have allowed for a better understanding of the catalytic cycle of this remarkable transformation, which occurs by a distinct reaction mechanism to that of the corresponding sp2 C[BOND]H bond functionalization. The hydrogen atom involved in the C[BOND]H activation process, a remarkably ‘facile’ step, is ultimately released as hydrogen gas.

    24. Anticancer Drugs

      Near-Infrared-Controlled, Targeted Hydrophobic Drug-Delivery System for Synergistic Cancer Therapy (pages 10388–10394)

      Xinjian Yang, Zhen Liu, Zhenhua Li, Fang Pu, Prof. Dr. Jinsong Ren and Prof. Dr. Xiaogang Qu

      Article first published online: 13 JUN 2013 | DOI: 10.1002/chem.201204624

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      Special delivery: A novel hydrophobic drug-delivery platform based on gold nanorods incorporated within a mesoporous silica framework has been developed. Near-infrared light (NIR) is used to control the release of encapsulated drug molecules. In vitro and in vivo experiments reveal that integration of chemotherapy and photothermotherapy into one system could be an efficient way to cure cancer with high spatial/temperal resolution (see scheme).

    25. Pi Interactions

      Kinetic Stabilization and Reactivity of π Single-Bonded Species: Effect of the Alkoxy Group on the Lifetime of Singlet 2,2-Dialkoxy-1,3-diphenyloctahydropentalene-1,3-diyls (pages 10395–10404)

      Tomoyuki Nakagaki, Tomoko Sakai, Tsutomu Mizuta, Yoshihisa Fujiwara and Prof. Manabu Abe

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300038

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      Singles club: Kinetic stabilization of π single-bonded species was achieved by introducing bulky alkoxy groups into the remote position of the π single-bonded moiety (see figure). The cis-selective formation of the ring-closing product was predicted by DFT computations.

    26. Palladium

      Pyracene-Linked Bis-Imidazolylidene Complexes of Palladium and Some Catalytic Benefits Produced by Bimetallic Catalysts (pages 10405–10411)

      Dr. Gregorio Guisado-Barrios, Joanna Hiller and Prof. Eduardo Peris

      Article first published online: 18 JUN 2013 | DOI: 10.1002/chem.201300486

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      Two is better than one: The catalytic activity of two dipalladium complexes with a pyracene-linked bis-imidazolylidene bridging ligand has been compared with the related monopalladium complexes in the acylation of aryl halides and Suzuki–Miyaura C[BOND]C coupling (see figure). The dimetallic catalysts show enhanced catalytic activity relative to the monometallic ones.

    27. Hydrogenation

      Frustrated Lewis Pair Chemistry of Chiral (+)-Camphor-Based Aminoboranes (pages 10412–10418)

      Markus Lindqvist, Dr. Kirill Axenov, Dr. Martin Nieger, Dr. Minna Räisänen, Prof. Markku Leskelä and Prof. Timo Repo

      Article first published online: 20 JUN 2013 | DOI: 10.1002/chem.201300462

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      Bor(o)n to be wild: Dimethylamino-(+)-camphorenamine reacted with an equimolar amount of Piers' borane to give the corresponding iminium–hydroborate zwitterionic salt (see scheme). Being in equilibrium with the parent enamine–HB(C6F5)2 N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the iminium group in the molecule. When the starting enamine is present in excess, hydrogenation of the camphor–enamine framework proceeds in a catalytic fashion.

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