Chemistry - A European Journal

Cover image for Vol. 19 Issue 37

September 9, 2013

Volume 19, Issue 37

Pages 12173–12559

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. You have free access to this content
      Cover Picture: Physical Properties of Superbulky Lanthanide Metallocenes: Synthesis and Extraordinary Luminescence of [EuII(CpBIG)2] (CpBIG=(4-nBu-C6H4)5-Cyclopentadienyl) (Chem. Eur. J. 37/2013) (page 12173)

      Prof. Dr. Sjoerd Harder, Dominik Naglav, Dr. Christian Ruspic, Prof. Dr. Claudia Wickleder, Dr. Matthias Adlung, Dr. Wilfried Hermes, Dr. Matthias Eul, Prof. Dr. Rainer Pöttgen, Dr. Daniel B. Rego, Prof. Dr. Frederic Poineau, Prof. Dr. Kenneth R. Czerwinski, Prof. Dr. Rolfe H. Herber and Prof. Dr. Israel Nowik

      Article first published online: 2 SEP 2013 | DOI: 10.1002/chem.201390139

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      High luminescence is observed for an Eu2+ ion sandwiched between two bulky cyclopentadienyl ligands, as described by S. Harder et al. in their Full Paper on page 12272 ff. In contrast to [Eu(Cp*)2] (Cp* = pentamethylcyclopentadienyl), which hardly shows luminescence, a quantum yield of 45% is found for the europocene [Eu(CpBIG)2] (CpBIG=(4-nBu-C6H4)5-cyclopentadienyl). Magnetic susceptibility measurements, and Mössbauer as well as EXAFS spectroscopy rule out possible oxidation-state ambiguities for the lanthanide(II) metallocenes of Sm, Eu, and Yb.

    2. You have free access to this content
      Inside Cover: Structural and Dynamic Properties of Monoclonal Antibodies Immobilized on CNTs: A Computational Study (Chem. Eur. J. 37/2013) (page 12174)

      Federica De Leo, Dr. Jacopo Sgrignani, Prof. Davide Bonifazi and Dr. Alessandra Magistrato

      Article first published online: 2 SEP 2013 | DOI: 10.1002/chem.201390140

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      All-atom explicit solvent molecular dynamics (MD)  simulations used to investigate the structural and dynamic properties of a bioconjugate hybrid are reported by D. Bonifazi, A. Magistrato et al. in their Full Paper on p. 12281 ff. This hybrid contains a monoclonal Cetuximab antibody (Ctx) that is non-covalently adsorbed on a carbon nanotube exosurface. The simulations show that the antibody preferentially adopts a unique pose, in which a maximal exposure of the residues to the graphitic surface is accomplished.

    3. You have free access to this content
      Back Cover: Chlorophyll Breakdown in Senescent Banana Leaves: Catabolism Reprogrammed for Biosynthesis of Persistent Blue Fluorescent Tetrapyrroles (Chem. Eur. J. 37/2013) (page 12564)

      Clemens Vergeiner, Dr. Srinivas Banala and Prof. Dr. Bernhard Kräutler

      Article first published online: 2 SEP 2013 | DOI: 10.1002/chem.201390143

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      A stunning variety  of “hypermodified” blue fluorescent chlorophyll catabolites accumulates in senescent banana leaves, as reported by B. Kräutler et al. in the Full Paper on page 12294 ff. The cover shows a vertical cut through a yellow leaf, as seen by fluorescence microscopy, superimposed with the structures of chlorophyll a and of a major fluorescent catabolite. Colored halos highlight the transformation of red fluorescing chlorophylls to the blue fluorescing breakdown products.

  2. Graphical Abstract

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. You have free access to this content
      Corrigendum: Formation of a Metalloporphyrin-Based Nanoreactor by Postsynthetic Metal–Ion Exchange of a Polyhedral-Cage Containing a Metal–Metalloporphyrin Framework (page 12187)

      Dr. Xi-Sen Wang, Matthew Chrzanowski, Dr. Lukasz Wojtas, Dr. Yu-Sheng Chen and Prof. Dr. Shengqian Ma

      Article first published online: 2 SEP 2013 | DOI: 10.1002/chem.201303271

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

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

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

      Hollow-Shelled Nanoreactors Endowed with High Catalytic Activity (pages 12196–12211)

      Dr. Moisés Pérez-Lorenzo, Dr. Belén Vaz, Dr. Verónica Salgueiriño and Prof. Miguel A. Correa-Duarte

      Article first published online: 14 AUG 2013 | DOI: 10.1002/chem.201301802

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      Sleepy hollows wake up: The design of different hollow-shelled nanoreactors is reviewed, analyzing the effects of both the shells and the active metal nanoparticles on the overall catalytic efficiency. Attention is focused on the methods used to prepare these hybrid nanocomposites and their different applications. Future perspectives on innovative architectures and further uses in catalysis are also addressed.

  6. Communications

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

      Nickel-Catalyzed Chemo- and Stereoselective Alkenylative Cyclization of 1,6-Enynes with Alkenyl Boronic Acids (pages 12212–12216)

      Dr. Chun-Ming Yang, Dr. Subramaniyan Mannathan and Prof. Dr. Chien-Hong Cheng

      Article first published online: 21 AUG 2013 | DOI: 10.1002/chem.201302180

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      Discover nickel! A nickel-catalyzed alkenylative cyclization of 1,6-enynes and alkenyl boronic acids affording substituted pyrrolidines and dihydrofurans is described (see scheme; cod=1,5-cyclooctadiene, Ts = p-toluene sulfonate). The reaction is highly chemo- and stereoselective. A possible reaction mechanism involving a nickelacyclopentene intermediate is proposed.

    2. Protein–Protein Interactions

      Mapping Functional Interaction Sites of Human Prune C-Terminal Domain by NMR Spectroscopy in Human Cell Lysates (pages 12217–12220)

      Dr. Donatella Diana, Dr. Giovanni Smaldone, Dr. Pasquale De Antonellis, Dr. Luciano Pirone, Dr. MariaNeve Carotenuto, Dr. Alessandro Alonzi, Dr. Sonia Di Gaetano, Prof. Massimo Zollo, Dr. Emilia M. Pedone and Prof. Roberto Fattorusso

      Article first published online: 12 AUG 2013 | DOI: 10.1002/chem.201302168

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      Get well prune: The C-terminal third domain of h-prune is largely unfolded and involved in relevant protein–protein interactions, particularly with Nm23-H1 (see figure), GSK-3β and gelsolin. This study shows that protein functions mediated by protein–protein interactions can be accurately followed in cell lysates by using fast NMR spectroscopy, which could be easily used for a very efficient NMR drug-discovery strategy.

    3. NMR Spectroscopy

      Combining J-Edited and Correlation Spectroscopies Within a Multi-dimensional Spatial Frequency Encoding: Toward Fully Resolved 1H NMR Spectra (pages 12221–12224)

      Dr. Nicolas Giraud, Daisy Pitoux, Dr. Jean-Michel Ouvrard and Prof. Denis Merlet

      Article first published online: 12 AUG 2013 | DOI: 10.1002/chem.201302005

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      J-resolved at a glance: Passive coupling refocusing-COSY experiments based on a frequency encoding of the sample along two directions of space are presented. It allows various spin evolutions to be triggered in different parts of the sample in a selective and fully controlled manner. This yields 2D spectra in which the whole proton network appears as a series of fully resolved and straightforwardly assignable doublets, triplets or quartets (see figure).

    4. Cluster Compounds

      Novel Alkoxide Cluster Topologies Featuring Rare Seesaw Geometry at Transition Metal Centers (pages 12225–12228)

      James A. Bellow, Dong Fang, Natalija Kovacevic, Dr. Philip D. Martin, Prof. Jason Shearer, Prof. G. Andrés Cisneros and Prof. Stanislav Groysman

      Article first published online: 9 AUG 2013 | DOI: 10.1002/chem.201302558

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      Caution! Chemists playing: Novel clusters of the form [M2Li2Cl2(OR)4] featuring rare seesaw geometry at the transition metal centers were synthesized for M=Cr[BOND]Co. The use of sterically hindering alkoxide ligands, as well as the inclusion of lithium ions in the structures enforces this highly unusual configuration.

    5. Coupling Reactions

      Tertiary Amines as Synthetic Equivalents of Vinyl Cations: Zinc Bromide Promoted Coupling of Propargylamines with α-Isocyanoacetamides To Give 2,4,5-Trisubstituted Oxazoles Initiated by an Internal Redox Process (pages 12229–12233)

      Dr. Yann Odabachian, Dr. Qian Wang and Prof. Dr. Jieping Zhu

      Article first published online: 14 AUG 2013 | DOI: 10.1002/chem.201302106

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      Crabée interrupted: Propargylamines 1 react with α-isocyanoacetamides 2 in the presence of zinc bromide to afford vinyl oxazoles 3. The transformation, wherein the propargylamine acts as a vinyl cation synthetic equivalent, involves a domino sequence incorporating a 1,5-hydride shift, intermolecular trapping/cyclization, and a 1,6-elimination (see scheme).

    6. NMR Spectroscopy

      A Well-Defined Pd Hybrid Material for the Z-Selective Semihydrogenation of Alkynes Characterized at the Molecular Level by DNP SENS (pages 12234–12238)

      Dr. Matthew P. Conley, Ruben M. Drost, Dr. Mathieu Baffert, Dr. David Gajan, Prof. Dr. Cornelis Elsevier, Dr. W. Trent Franks, Prof. Dr. Hartmut Oschkinat, Laurent Veyre, Alexandre Zagdoun, Dr. Aaron Rossini, Dr. Moreno Lelli, Dr. Anne Lesage, Dr. Gilles Casano, Dr. Olivier Ouari, Prof. Dr. Paul Tordo, Prof. Dr. Lyndon Emsley, Prof. Dr. Christophe Copéret and Dr. Chloé Thieuleux

      Article first published online: 19 AUG 2013 | DOI: 10.1002/chem.201302484

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      Direct evidence of the conformation of a Pd–N heterocyclic carbene (NHC) moiety imbedded in a hybrid material and of the Pd–NHC bond were obtained by dynamic nuclear polarization surface-enhanced NMR spectroscopy (DNP SENS) at natural abundance in short experimental times (hours). Overall, this silica-based hybrid material containing well-defined Pd–NHC sites in a uniform environment displays high activity and selectivity in the semihydrogenation of alkynes into Z-alkenes (see figure).

    7. Digold Catalysts

      Air-Stable, Dinuclear and Tetranuclear σ,π-Acetylide Gold(I) Complexes and Their Catalytic Implications (pages 12239–12244)

      Dr. Abdessamad Grirrane, Prof. Dr. Hermenegildo Garcia, Prof. Dr. Avelino Corma and Dr. Eleuterio Álvarez

      Article first published online: 9 AUG 2013 | DOI: 10.1002/chem.201301623

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      Two for one gold: Factors governing the formation of isolable digold(I) σ,π-acetylide complexes are given (see scheme), indicating the general tendency of phosphine–AuI precatalysts to form this type of complexes, which are involved as reaction intermediates in gold(I)-catalyzed reactions. Mechanistic insights into the intermolecular hydroamination of aniline and terminal alkynes catalyzed by gold(I) have shown the role of a fluxional, cationic σ,π-digold alkynide complex as one of the intermediates in the formation of imines.

    8. Catalysis

      A General Palladium-Catalyzed Carbonylative Synthesis of Chromenones from Salicylic Aldehydes and Benzyl Chlorides (pages 12245–12248)

      Dr. Xiao-Feng Wu, Lipeng Wu, Dr. Ralf Jackstell, Dr. Helfried Neumann and Prof. Matthias Beller

      Article first published online: 12 AUG 2013 | DOI: 10.1002/chem.201301774

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      Cute CO! An interesting and straightforward procedure for the carbonylative synthesis of chromenones from readily available salicylic aldehydes and benzyl chlorides has been developed (see scheme; DPPP=1,3-bis(diphenylphosphino)propane). In the presence of a palladium catalyst, various coumarins were produced in good to excellent yields.

    9. Diversity-Oriented Synthesis

      Efficient Metal-Free Synthesis of Various Pyrido[2′,1′:2,3]imidazo- [4,5-b]quinolines (pages 12249–12253)

      Mathieu Arnould, Dr. Marie-Aude Hiebel, Dr. Stéphane Massip, Prof. Jean Michel Léger, Prof. Christian Jarry, Prof. Sabine Berteina-Raboin and Prof. Gérald Guillaumet

      Article first published online: 16 AUG 2013 | DOI: 10.1002/chem.201300961

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      Dancing with diversity: The synthesis of diverse pyrido[2′,1′:2,3]imidazo[4,5-b]quinolines bearing several substitution patterns was developed based on combining a multicomponent reaction (Groebke–Blackburn–Bienaymé reaction) with an original cyclization as a secondary transformation (see scheme; DBU=1,8-diazabicyclo[5.4.0]undec-7-ene).

    10. Lanthanide Oxide Clusters

      Lanthanide Oxide Clusters: From Tetrahedral [Dy44-O)]10+ to Supertetrahedral [Ln204-O)11]38+ (Ln=Tb, Dy, Ho, Er) (pages 12254–12258)

      Wei-Quan Lin, Xiao-Fen Liao, Jian-Hua Jia, Ji-Dong Leng, Jun-Liang Liu, Fu-Sheng Guo and Prof. Dr. Ming-Liang Tong

      Article first published online: 21 JUN 2013 | DOI: 10.1002/chem.201301397

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      Supertetrahedral clusters: A family of lanthanide oxide supertetrahedral T3 {Ln20} clusters (Ln=Tb, Dy, Ho, Er; see figure) were obtained from the solvothermal reaction of lanthanide(III) salts with polytriazolate ligands that could be methylated and oxidized in situ.

    11. Ultrasmall Nanoparticles

      Exclusive synthesis of Au11(PPh3)8Br3 against the Cl Analogue and the Electronic Interaction between Cluster Metal Core and Surface Ligands (pages 12259–12263)

      Prof. Dr. Zhikun Wu and Prof. Dr. Rongchao Jin

      Article first published online: 13 AUG 2013 | DOI: 10.1002/chem.201300592

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      To goldly go…: Exclusive Au11(PPh3)8Br3 (see illustration) formation was obtained by a novel two-phase method, although the molar ratio of Br/Cl was 1:4, as identified by ESI-MS. Interestingly, the interaction of Au11 core electrons with the benzene π electrons of the phosphine ligands was revealed by NMR spectroscopy and optical absorption spectroscopic analyses.

  7. Full Papers

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

      A Unique Au–Ag–Au Triangular Motif in a Trimetallic Halonium Dication: Silver Incorporation in a Gold(I) Catalyst (pages 12264–12271)

      Yuyang Zhu, Dr. Cynthia S. Day, Lin Zhang, Katarina J. Hauser and Prof. Amanda C. Jones

      Article first published online: 9 AUG 2013 | DOI: 10.1002/chem.201302152

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      Silver lining! As a result of explorations into the solution chemistry of silver/gold mixtures, a unique trimetallic chloronium dication was discovered that incorporates silver–arene chelation and a triangular mixed gold/silver core (see figure). Notably, it was isolated from a previously Celite-filtered solution, a procedure generally believed to be efficient at removing silver. The solid-state and solution structure, as well as DFT calculations are reported herein.

    2. Lanthanide Chemistry

      Physical Properties of Superbulky Lanthanide Metallocenes: Synthesis and Extraordinary Luminescence of [EuII(CpBIG)2] (CpBIG=(4-nBu-C6H4)5-Cyclopentadienyl) (pages 12272–12280)

      Prof. Dr. Sjoerd Harder, Dominik Naglav, Dr. Christian Ruspic, Prof. Dr. Claudia Wickleder, Dr. Matthias Adlung, Dr. Wilfried Hermes, Dr. Matthias Eul, Prof. Dr. Rainer Pöttgen, Dr. Daniel B. Rego, Prof. Dr. Frederic Poineau, Prof. Dr. Kenneth R. Czerwinski, Prof. Dr. Rolfe H. Herber and Prof. Dr. Israel Nowik

      Article first published online: 31 JUL 2013 | DOI: 10.1002/chem.201302021

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      Superbulky metallocenes: [M(CpBIG)2] (M=Sm, Eu, Yb; CpBIG=(4-nBu-C6H4)5-cyclopentadienyl). Temperature-dependent magnetic susceptibility, Mössbauer, XANES and luminescence measurements show a true +II oxidation state for the metal. [Eu(CpBIG)2]II displays an extraordinary orange luminescence (see figure) with 45 % quantum yield.

    3. Molecular Dynamics

      Structural and Dynamic Properties of Monoclonal Antibodies Immobilized on CNTs: A Computational Study (pages 12281–12293)

      Federica De Leo, Dr. Jacopo Sgrignani, Prof. Davide Bonifazi and Dr. Alessandra Magistrato

      Article first published online: 24 JUL 2013 | DOI: 10.1002/chem.201301376

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      Antibodies and carbon nanotubes (CNT): Molecular dynamics simulations on the structural and dynamic properties of an antibody interfacing with a CNT surface showed that the hydrophobic interactions mainly govern the adsorption of the protein on the graphitic surface. The predicted structural models are consistent with the experimental data, supporting the reliability of the bioconjugation strategy for engineering active hybrid nanomaterials for therapeutic applications.

    4. Chlorophyll Metabolism

      You have full text access to this OnlineOpen article
      Chlorophyll Breakdown in Senescent Banana Leaves: Catabolism Reprogrammed for Biosynthesis of Persistent Blue Fluorescent Tetrapyrroles (pages 12294–12305)

      Clemens Vergeiner, Dr. Srinivas Banala and Prof. Dr. Bernhard Kräutler

      Article first published online: 14 AUG 2013 | DOI: 10.1002/chem.201301907

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      Blue luminescent leaves: Because of a surprising, massive accumulation of fluorescent chlorophyll catabolites (FCCs), yellow senescent leaves of the banana plant (Musa acuminata, see figure) luminesce blue. In these leaves, chlorophyll breakdown is reprogrammed by enzymatic FCC-esterification with (substituted) glycopyranose moieties.

    5. Energy Storage

      Porous Nitrogen-Doped Carbon Nanotubes Derived from Tubular Polypyrrole for Energy-Storage Applications (pages 12306–12312)

      Guiyin Xu, Bing Ding, Ping Nie, Laifa Shen, Jie Wang and Prof. Xiaogang Zhang

      Article first published online: 23 JUL 2013 | DOI: 10.1002/chem.201301352

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      Rich man, pore man: Porous nitrogen-doped carbon nanotubes (PNCNT) that are derived from a tubular polypyrrole (T-PPY) exhibit great potential for both electrical double-layer supercapacitors and lithium-sulfur batteries (see scheme).

    6. Molecular Rotors

      Molecular Rotors of Coronene in Charge-Transfer Solids (pages 12313–12324)

      Dr. Yukihiro Yoshida, Dr. Yasuhiro Shimizu, Dr. Takeshi Yajima, Dr. Goro Maruta, Prof. Dr. Sadamu Takeda, Dr. Yoshiaki Nakano, Dr. Takaaki Hiramatsu, Prof. Dr. Hiroshi Kageyama, Prof. Dr. Hideki Yamochi and Prof. Dr. Gunzi Saito

      Article first published online: 29 JUL 2013 | DOI: 10.1002/chem.201300578

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      Molecular rotation: Neutral charge-transfer complexes of coronene (electron donor, D; see figure, mnt=maleonitriledithiolate) were obtained with various π-planar electron acceptors (A), and the rotor behavior of the complexes with various molecular arrangements was investigated. A non-parallel arrangement of coronenes within a DDA-type alternating column has a favorable effect on the in-plane rotation of the coronenes.

    7. Cytosine-Based Conductors

      Charge-Transfer Solids Using Nucleobases: Supramolecular Architectures Composed of Cytosine and [Ni(dmit)2] Assembled by Multiple Hydrogen Bonds and Heteroatomic Contacts (pages 12325–12335)

      Dr. Yukihiro Yoshida, Dr. Mitsuhiko Maesato, Dr. Manabu Ishikawa, Dr. Yoshiaki Nakano, Dr. Takaaki Hiramatsu, Prof. Dr. Hideki Yamochi and Prof. Dr. Gunzi Saito

      Article first published online: 29 JUL 2013 | DOI: 10.1002/chem.201300865

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      Nucleobase-based conductors: Various combinations between the nucleobase cytosine (C) with different protonation states and [Ni(dmit)2] (dmit=1,3-dithiole-2-thione-4,5-dithiolate) with different redox states afforded four salts with dissimilar supramolecular motifs and electronic properties. Especially, the unprecedented corrugated 2D sheet of hemiprotonated CHC+ units afforded the first metallic salt that contains a mixed-valent metal complex anion combined with a nucleobase cation.

    8. Macrocycles

      Synthesis of a Strained Acetylenic Macrocycle Incorporating a para-Oligo[2]cruciform Bridge Bent over Nanoscopic Dimensions: Structural, Electronic, Spectroscopic, and Ion-Sensing Properties (pages 12336–12349)

      Dr. Paul N. W. Baxter, Dr. Jean-Paul Gisselbrecht, Dr. Lydia Karmazin-Brelot, Prof. Alexandre Varnek and Dr. Lionel Allouche

      Article first published online: 23 JUL 2013 | DOI: 10.1002/chem.201204569

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      Reining in the strain: An Eglinton–Galbraith diethyne cyclization yielded an unusual bow-shaped cycle (see scheme), incorporating a strained yet stable conjugated oligo[2]cruciform wire, bent over nanoscopic dimensions by a terpyridine tether. As well as spectroscopically sensing metal ions, it undergoes thermo-controllable bandgap changes in solution, consistent with hindered relative twisting of the substituted phenyl rings, thus functioning as an environmentally adaptive conjugation switch.

    9. Asymmetric Catalysis

      Validity of Inorganic Nanosheets as an Efficient Planar Substituent To Enhance the Enantioselectivity of Transition-Metal-Catalyzed Asymmetric Synthesis (pages 12350–12355)

      Li-Wei Zhao, Hui-Min Shi, Zhe An, Jiu-Zhao Wang and Prof. Jing He

      Article first published online: 23 JUL 2013 | DOI: 10.1002/chem.201301150

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      Magic planar substituent: The crucial role of the layered double hydroxide (LDH) layer as a planar substituent of attached α-amino acid ligand in the enantioselective improvement of transition-metal-catalyzed asymmetric synthesis has been revealed (see figure).

    10. Supramolecular Gels

      Synthesis and Self-Assembly of NCN-Pincer Pd-Complex-Bound Norvalines (pages 12356–12375)

      Kazuki Ogata, Daisuke Sasano, Tomoya Yokoi, Dr. Katsuhiro Isozaki, Ryota Yoshida, Dr. Toshio Takenaka, Dr. Hirofumi Seike, Dr. Tetsuya Ogawa, Prof. Dr. Hiroki Kurata, Dr. Nobuhiro Yasuda, Prof. Dr. Hikaru Takaya and Prof. Dr. Masaharu Nakamura

      Article first published online: 1 AUG 2013 | DOI: 10.1002/chem.201301513

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      Metalated amino acids: A series of NCN-pincer Pd-complex-bound norvaline derivatives was successfully synthesized without loss of the optical purity and Pd unit. Efficient self-assembly properties of these Pd–norvalines were found to afford well-regulated Pd arrays both in the single crystal and in the supramolecular gel. A solvent-dependent configuration control of the Pd array was corroborated by means of single-crystal X-ray crystallography and cryo-TEM analysis.

    11. Ruthenium Oligomers

      A Combined Experimental and Computational Study of Linear Ruthenium(II) Coordination Oligomers with End-Capping Organic Redox Sites: Insight into the Light Absorption and Charge Delocalization (pages 12376–12387)

      Chang-Jiang Yao, Dr. Ren-Hui Zheng, Hai-Jing Nie, Bin-Bin Cui, Prof. Dr. Qiang Shi, Prof. Dr. Jiannian Yao and Prof. Dr. Yu-Wu Zhong

      Article first published online: 6 AUG 2013 | DOI: 10.1002/chem.201301319

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      Amine-decorated Ru oligomers: Linear Ru coordination oligomers capped with one or two di-p-anisylamino-substituted terpyridine ligands (see figure) have been synthesized and studied. These complexes display enhanced light absorption with respect to model complexes without terminal amine units. Upon one-electron oxidation of the amine-substituted Ru complexes, metal-to-nitrogen charge-transfer transitions have been observed.

    12. Nanoparticles

      Mesoporous Core–Shell Fenton Nanocatalyst: A Mild, Operationally Simple Approach to the Synthesis of Adipic Acid (pages 12388–12395)

      Astam K. Patra, Arghya Dutta and Prof. Dr. Asim Bhaumik

      Article first published online: 12 AUG 2013 | DOI: 10.1002/chem.201301498

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      Mesoporous core–shell particles: Mesoporous nanoparticles composed of γ-Al2O3 cores and α-Fe2O3 shells were synthesized in aqueous medium. The Al2O3@Fe2O3 core–shell nanoparticles act as a heterogeneous Fenton nanocatalyst in the presence of hydrogen peroxide, and show high catalytic efficiency for the conversion of cyclohexanone to adipic acid in water in one step (see figure).

    13. Structure Determination

      A Study of Transition-Metal Organometallic Complexes Combining 35Cl Solid-State NMR Spectroscopy and 35Cl NQR Spectroscopy and First-Principles DFT Calculations (pages 12396–12414)

      Dr. Karen E. Johnston, Christopher A. O'Keefe, Dr. Régis M. Gauvin, Dr. Julien Trébosc, Dr. Laurent Delevoye, Prof. Jean-Paul Amoureux, Dr. Nicolas Popoff, Dr. Mostafa Taoufik, Dr. Konstantin Oudatchin and Prof. Robert W. Schurko

      Article first published online: 1 AUG 2013 | DOI: 10.1002/chem.201301268

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      Fast and furious: A series of transition-metal organometallic complexes with commonly occurring metal[BOND]chlorine bonding motifs were characterized using a combination of 35Cl solid-state NMR (SSNMR) spectroscopy, 35Cl nuclear quadrupole resonance (NQR) spectroscopy and first-principles density functional theory (DFT) calculations. Static 35Cl ultra-wideline NMR spectra were rapidly acquired in a piecewise manner at high magnetic field strengths.

    14. Asymmetric Synthesis

      Absolute Asymmetric Synthesis of Enantiopure Organozinc Reagents, Followed by Highly Enantioselective Chlorination (pages 12415–12423)

      Susanne Olsson, Dr. Anders Lennartson and Prof. Mikael Håkansson

      Article first published online: 23 JUL 2013 | DOI: 10.1002/chem.201301465

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      AAS easy as ABC: The absolute asymmetric synthesis (AAS) of indenylzinc reagents is reported through total spontaneous resolution followed by enantiospecific conversion into 1-chloroindene (see scheme, NCS = N-chlorosuccinimide). The general AAS method offers easy access to both enantiomers and an almost limitless variation in the design of the product.

    15. RNA

      Intramolecular Participation of Amino Groups in the Cleavage and Isomerization of Ribonucleoside 3′-Phosphodiesters: The Role in Stabilization of the Phosphorane Intermediate (pages 12424–12434)

      Luigi Lain, Prof. Dr. Harri Lönnberg and Dr. Tuomas Lönnberg

      Article first published online: 29 JUL 2013 | DOI: 10.1002/chem.201301711

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      Amino accelerator: Intramolecular amino groups promote cleavage and isomerization of ribonucleoside phosphodiester bonds in both protonated and deprotonated forms. The most likely mechanistic explanation is facilitation of the first step of the reaction, that is, formation of the cyclic phosphorane intermediate, by concomitant proton transfer. The magnitude of this facilitation differs greatly between the 2′- and 3′-isomers (see figure).

    16. Redox Chemistry

      Proton Catalysis in the Redox Responsivity of a Mini-Sized Photochromic Diarylethene (pages 12435–12445)

      Dr. Julie Massaad, Dr. Jean-Claude Micheau, Dr. Christophe Coudret, Dr. Charles Louis Serpentini and Dr. Gonzalo Guirado

      Article first published online: 23 JUL 2013 | DOI: 10.1002/chem.201301566

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      From vice to virtue: Combined cyclic voltammetry and kinetic modeling have revealed an autocatalytic mechanistic scenario for the oxidative, thermal ring-opening of the closed photoisomer of a mini-sized photochromic diarylethene by a copper(II) salt in acetonitrile (see figure). Initially there is a CuII wastage without ring opening and possible degradation; later, the acid building-up from the CuII reduction into CuI triggers a propagation cycle during which the colored isomer ring opens without CuII consumption.

    17. Energetic Materials

      Ionic Liquids as Unique Solvents in One-Pot Synthesis of 4-(N,2,2,2-Tetranitroethylamino)-3-R-Furazans (pages 12446–12457)

      Prof. Aleksei B. Sheremetev, Nataly S. Aleksandrova, Nadezhda V. Palysaeva, Marina I. Struchkova, Vladimir A. Tartakovsky and Kyrill Yu. Suponitsky

      Article first published online: 29 JUL 2013 | DOI: 10.1002/chem.201302126

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      A safe and effective two-step one-pot protocol for the synthesis of N-nitrated trinitroethylamino furazans in good yields has been developed. Initially, the route involves the condensation of aminofurazans with trinitroethanol, followed by the N-nitration of intermediate Mannich base in ionic liquids (ILs; see scheme).

    18. Ambipolar Semiconductors

      Molecular and Electronic-Structure Basis of the Ambipolar Behavior of Naphthalimide–Terthiophene Derivatives: Implementation in Organic Field-Effect Transistors (pages 12458–12467)

      Dr. Rocío Ponce Ortiz , Dr. Helena Herrera, Prof. María J. Mancheño, Prof. Carlos Seoane, Prof. José L. Segura, Paula Mayorga Burrezo, Prof. Juan Casado, Prof. J. Teodomiro López Navarrete, Dr. Antonio Facchetti and Prof. Tobin J. Marks

      Article first published online: 24 JUL 2013 | DOI: 10.1002/chem.201301489

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      Tailoring ambipolarity: A new family of completely planar naphthalimide-fused thienopyrazine derivatives in which coplanarity is enforced by intramolecular S⋅⋅⋅N interactions has been synthesized for ambipolar charge transport in organic field-effect transistors and analyzed by vibrational spectroscopy and DFT calculations. Their data are compared with those previously reported for a series of planar and twisted thiophene–naphthalene derivatives (see figure) and afford new understanding of OFET performance in this general class of molecular semiconductors.

    19. Carbonyl Complexes

      A Systematic Investigation of Coinage Metal Carbonyl Complexes Stabilized by Fluorinated Alkoxy Aluminates (pages 12468–12485)

      Dipl.-Chem. Julia Schaefer, Dipl.-Chem. Anne Kraft, Stefanie Reininger, Dr. Gustavo Santiso-Quinones, Dr. Daniel Himmel, Dr. Nils Trapp, Dipl.-Chem. Urs Gellrich, Prof. Dr. Bernhard Breit and Prof. Dr. Ingo Krossing

      Article first published online: 29 JUL 2013 | DOI: 10.1002/chem.201204544

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      Precious carbonyl complexes: CuI, AgI, and AuI salts react with carbon monoxide in the presence of weakly coordinating anions to known and structurally new non-classical coinage metal carbonyl complexes [M(CO)n][A] (A=fluorinated alkoxy aluminate anions). The first structurally characterized copper(I) triscarbonyl complexes, for example, [Cu(CO)3(CH2Cl2)]+, and the A-frame [Au2(CO)2Cl]+ were prepared (see figure).

    20. Hydrogels

      Pristine Carbon-Nanotube-Included Supramolecular Hydrogels with Tunable Viscoelastic Properties (pages 12486–12496)

      Subhra Kanti Mandal, Tanmoy Kar and Prof. Prasanta Kumar Das

      Article first published online: 23 JUL 2013 | DOI: 10.1002/chem.201300302

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      Tubes included: Amino acid/dipeptide-based amphiphilic hydrogelators with an imidazolium head group incorporate large amounts of single-walled carbon nanotubes (SWNTs) without compromising their intrinsic properties. Remarkable enhancement (ca. 85-fold) in the mechanical rigidity of the resulting soft nanocomposite is observed, which can be modulated by varying the amount of incorporated SWNTs (see figure).

    21. Carbohydrates

      Automated Solid-Phase Synthesis of a β-(1,3)-Glucan Dodecasaccharide (pages 12497–12503)

      Markus W. Weishaupt, Stefan Matthies and Prof. Dr. Peter H. Seeberger

      Article first published online: 16 AUG 2013 | DOI: 10.1002/chem.201204518

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      β-Glucans are a group of structurally heterogeneous polysaccharides found in bacteria, fungi, algae and plants. The first automated solid-phase synthesis of a β-glucan oligosaccharide is reported. A β-(1,3)-glucan dodecasaccharide was assembled in 56 h in a stereoselective fashion with an average yield of 88 % per step (see scheme; Fmoc = 9-fluorenylmethoxycarbonyl, PIV = pivaloyl).

    22. Gold Catalysis

      From Ynamides to Highly Substituted Benzo[b]furans: Gold(I)-Catalyzed 5-endo-dig-Cyclization/Rearrangement of Alkylic Oxonium Intermediates (pages 12504–12511)

      Maria Camila Blanco Jaimes, Vanessa Weingand, Dr. Frank Rominger and Prof. Dr. A. Stephen K. Hashmi

      Article first published online: 6 AUG 2013 | DOI: 10.1002/chem.201301595

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      Golden touch: Arylynamides with o-alkyloxy groups were prepared through an alkylation/cross-coupling/amidation sequence. Their Au-catalyzed conversion provided benzofurans with amine groups at the 2-position and alkyl groups at the 3-position.

    23. Chemoselectivity

      Chemoselectivity Control: Gold(I)-Catalyzed Synthesis of 6,7-Dihydrobenzofuran-4(5H)-ones and Benzofurans from 1-(Alkynyl)-7-oxabicyclo[4.1.0]heptan-2-ones (pages 12512–12516)

      Tao Wang, Shuai Shi, Dr. Mie Højer Vilhelmsen, Tuo Zhang, Dr. Matthias Rudolph, Dr. Frank Rominger  and Prof. Dr. A. Stephen K. Hashmi 

      Article first published online: 23 JUL 2013 | DOI: 10.1002/chem.201301698

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      Complete chemoselectivity control of gold(I)-catalyzed transformations of 1-(arylethynyl)-7-oxabicyclo[4.1.0]heptan-2-ones, which can be achieved by changing the ligand of the gold catalyst, allows two different products to be obtained from the same starting material, namely, 6,7-dihydrobenzofuran-4(5H)-ones and benzofurans (see scheme), both of which are potent building blocks for synthetic chemistry. IPr: 1,3-bis(diisopropylphenyl)imidazol-2-ylidene.

    24. Aryl-Substituted Tetrathiafulvalenes

      Molecular and Crystal Structure Diversity, and Physical Properties of Tetrathiafulvalene Derivatives Substituted with Various Aryl Groups through Sulfur Bridges (pages 12517–12525)

      Jibin Sun, Xiaofeng Lu, Jiafeng Shao, Xuexiang Li, Shangxi Zhang, Baolin Wang, Jinlian Zhao, Dr. Yongliang Shao, Dr. Ran Fang, Prof. Dr. Zhaohui Wang, Prof. Dr. Wei Yu and Prof. Dr. Xiangfeng Shao

      Article first published online: 5 AUG 2013 | DOI: 10.1002/chem.201301819

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      Structural diversity due to flexible linkers: A thorough investigation of the properties and structural diversity of tetrathiafulvalene (TTF) derivatives substituted with various aryl groups through sulfur bridges is reported (see graphic). The aryl groups significantly affect both the electronic and crystallographic properties of the TTFs. These TTFs are candidates as electronic materials, as well as functional building blocks for supramolecular assembly.

    25. Polymerization

      Metal-Free Polymerization of Phenylsilane: Tris(pentafluorophenyl)borane-Catalyzed Synthesis of Branched Polysilanes at Elevated Temperatures (pages 12526–12536)

      Dr. Andreas Feigl, Dr. Ion Chiorescu, Katrin Deller, Sven U. H. Heidsieck, Dr. Magnus R. Buchner, Dr. Virve Karttunen, Dr. Andreas Bockholt, Dr. Alexander Genest, Prof. Dr. Notker Rösch and Prof. Dr. Bernhard Rieger

      Article first published online: 26 JUL 2013 | DOI: 10.1002/chem.201203139

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      Polysilanes without metals! The strong organoborane Lewis acid B(C6F5)3 catalyzes the polymerization of phenylsilane at elevated temperatures (see scheme). 2D NMR spectroscopy revealed the resulting polymer to have a branched and highly substituted structure. DFT calculations confirmed the experimental results of this metal-free synthesis with substitution and branching being kinetically more favorable processes than Si[BOND]Si bond formation for linear growth.

    26. Bismuth Carboxylates

      Bismuth Tri- and Tetraarylcarboxylates: Crystal Structures, In Situ X-ray Diffraction, Intermediates and Luminescence (pages 12537–12546)

      Dr. Mark Feyand, Milan Köppen, Prof. Dr. Gernot Friedrichs and Prof. Dr. Norbert Stock

      Article first published online: 29 JUL 2013 | DOI: 10.1002/chem.201301139

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      High-throughput experiments have led to the discovery of five new bismuth carboxylates. Reaction conditions such as the metal/linker molar ratio play a crucial role in determining which compound is stable. In situ energy-dispersive X-ray diffraction (EDXRD, see figure) gave deeper insight into the crystallisation of these bismuth carboxylates, the luminescence properties of which are dominated by a combination of short-lived linker luminescence and long-lived Bi3+ luminescence.

    27. DNA

      Development of a Metal-Ion-Mediated Base Pair for Electron Transfer in DNA (pages 12547–12552)

      Dr. Thomas Ehrenschwender, Dr. Wolfgang Schmucker, Christian Wellner, Dipl.-Chem. Timo Augenstein, Dr. Patrick Carl, Dr. Jeffrey Harmer, Prof. Dr. Frank Breher and Prof. Dr. Hans-Achim Wagenknecht

      Article first published online: 26 JUL 2013 | DOI: 10.1002/chem.201300593

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      Ace of base: DNA duplex stability can be significantly increased by coordinating CuII ions to hydroxyquinoline base pairs (metal-mediated base pairing; see scheme). Fluorescence studies with a donor–DNA–acceptor system indicate that photoinduced charge-transfer processes across these metal-ion-mediated base pairs in DNA occur more efficiently than over natural base pairs.

    28. Spiro Compounds

      Highly Efficient Construction of Bisspirooxindoles Containing Vicinal Spirocenters through an Organocatalytic Modified Feist–Bénary Reaction (pages 12553–12559)

      Somayeh Ahadi, Hamid Reza Khavasi and Dr. Ayoob Bazgir

      Article first published online: 6 AUG 2013 | DOI: 10.1002/chem.201301175

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      Crowded spaces! An organocatalytic modified Feist–Bénary reaction of cyclic dicarbonyl compounds, isatins, and cyclic α-bromo dicarbonyls was developed. This method affords bisspirooxindole-fused dihydrofurans containing two vicinal spiro centers (see scheme; DBU=1,8-diazabicyclo[5.4.0]undec-7-ene). Employing cyclic α-halo dicarbonyl compounds for the synthesis of bisspirooxindole-fused dihydrofurans has not been previously reported.

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