Chemistry - A European Journal

Cover image for Vol. 20 Issue 6

February 3, 2014

Volume 20, Issue 6

Pages 1461–1764

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. You have free access to this content
      Cover Picture: Insertion of a Single-Molecule Magnet inside a Ferromagnetic Lattice Based on a 3D Bimetallic Oxalate Network: Towards Molecular Analogues of Permanent Magnets (Chem. Eur. J. 6/2014) (page 1461)

      Dr. Miguel Clemente-León, Prof. Eugenio Coronado, Prof. Carlos J. Gómez-García, Dr. Maurici López-Jordà, Dr. Agustín Camón, Ana Repollés and Dr. Fernando Luis

      Version of Record online: 28 JAN 2014 | DOI: 10.1002/chem.201490018

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      The concept of mixing a highly anisotropic system with a soft magnet, which is the approach commonly used to fabricate permanent magnets with large magnetic hysteresis, can also be developed in the molecular world. Instead of preparing metallic alloys formed by 3d metals with anisotropic lanthanides (such as NdFe14B), a molecular approach was used to design a hybrid crystalline lattice formed by an anisotropic single molecule magnet (SMM) incorporated into a bimetallic oxalate 3D ferromagnetic network. Thanks to the antiferromagnetic interaction established between these two magnetic networks, a large increase in the coercive field has been observed at low temperatures. For more details, see the Full Paper on page 1669 ff. by M. Clemente-León et al.

    2. You have free access to this content
      Inside Cover: A Pyrimidopyrimidine Janus-AT Nucleoside with Improved Base-Pairing Properties to both A and T within a DNA Duplex: The Stabilizing Effect of a Second Endocyclic Ring Nitrogen (Chem. Eur. J. 6/2014) (page 1462)

      Dr. Eric Largy, Wenbo Liu, Abid Hasan and Prof. David M. Perrin

      Version of Record online: 28 JAN 2014 | DOI: 10.1002/chem.201490019

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      A pyrimidopyrimidine Janus-AT nucleoside  NJAT displaying two complementary faces has been rationally designed to simultaneously base pair with A and T bases. NJAT forms stable Watson–Crick base pairs with either T or A, but is significantly destabilizing to duplex-DNA when paired with either a G or C base. In their Communication on page 1495 ff., D. M. Perrin et al. show that this optimized Janus-AT structure allows the selective targeting of AT base pairs and opens exciting prospects for sequence-specific DNA targeting.

    3. You have free access to this content
      Back Cover: Dormant versus Evolving Aminopalladated Intermediates: Toward a Unified Mechanistic Scenario in PdII-Catalyzed Aminations (Chem. Eur. J. 6/2014) (page 1768)

      Dr. Jamshid Rajabi, Mélanie M. Lorion, Vu Linh Ly, Dr. Frédéric Liron, Dr. Julie Oble, Prof. Dr. Guillaume Prestat and Prof. Dr. Giovanni Poli

      Version of Record online: 28 JAN 2014 | DOI: 10.1002/chem.201490022

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      When an alkene is complexed by PdX2 in the presence of a nucleophile, the resulting species exhibits a range of competing types of reactivity, such as alkene nucleopalladation or allylic C[BOND]H activation. In their Full Paper on page 1539 ff., G. Poli et al. show that an initial reversibly formed cyclic aminopalladated intermediate can either evolve along different pathways or stay dormant. In the latter case, alternative types of reactivity, such as allylic C[BOND]H activation or [3,3]-sigmatropic rearrangement can predominate.

  2. Cover Profile

    1. Top of page
    2. Cover Pictures
    3. Cover Profile
    4. Graphical Abstract
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    1. You have free access to this content
      Insertion of a Single-Molecule Magnet inside a Ferromagnetic Lattice Based on a 3D Bimetallic Oxalate Network: Towards Molecular Analogues of Permanent Magnets (page 1466)

      Dr. Miguel Clemente-León, Prof. Eugenio Coronado, Prof. Carlos J. Gómez-García, Dr. Maurici López-Jordà, Dr. Agustín Camón, Ana Repollés and Dr. Fernando Luis

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/chem.201304907

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      The integration of Mn2salen single molecule magnets into an oxalate ferromagnetic lattice gives rise to a hybrid material that, below 1 K, shows a sizeable magnetization hysteresis.” Read more about the story behind the cover in the Cover Profile and about the research itself on page 1669 ff. (DOI: 10.1002/chem.201303044)

  3. Graphical Abstract

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

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

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

      Supramolecular Approaches towards Ordered Polymer Materials (pages 1482–1489)

      Prof. Dr. Takashi Uemura

      Version of Record online: 17 JAN 2014 | DOI: 10.1002/chem.201303949

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      Polymer materials with ordered nanostructures have attracted considerable attention because of a wide variety of applications. Recent development of supramolecular chemistry has allowed fine and rational control over the organization of polymer chains (see figure).

  6. Communications

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

      Palladium-Catalyzed Aza-Wittig-Type Condensation of Isoxazol-5(4H)-ones with Aldehydes (pages 1490–1494)

      Dr. Kazuhiro Okamoto, Takuya Shimbayashi, Eisuke Tamura and Prof. Dr. Kouichi Ohe

      Version of Record online: 17 JAN 2014 | DOI: 10.1002/chem.201304211

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      New route to 2-azadienes: This paper describes the development of a palladium-catalyzed decarboxylative inter- and intramolecular condensation reaction of isoxazol-5(4 H)-ones with carbonyl compounds in the presence of PPh3, giving various 2-azabuta-1,3-dienes or pyrroles in moderate to high yields (see scheme).

    2. DNA Recognition

      A Pyrimidopyrimidine Janus-AT Nucleoside with Improved Base-Pairing Properties to both A and T within a DNA Duplex: The Stabilizing Effect of a Second Endocyclic Ring Nitrogen (pages 1495–1499)

      Dr. Eric Largy, Wenbo Liu, Abid Hasan and Prof. David M. Perrin

      Version of Record online: 17 JAN 2014 | DOI: 10.1002/chem.201303867

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      N-Game for DNA recognition: The synthesis and oligonucleotide incorporation of an optimized, soluble Janus-AT base (NJAT) that efficiently discriminates T/A over G/C bases, while retaining a nonprotonated state at physiological pH, is reported. NJAT was characterized in a duplex-DNA context with a set of biophysical and computational methods, all pointing out that this new base is a very good candidate for sequence-specific genome targeting (see figure).

    3. Polymerization

      Reversible Light-Driven Polymerization of Polyoxometalate Tethered with Coumarin Molecules (pages 1500–1504)

      UnSong Tong, Wei Chen, Dr. Chris Ritchie, Xiaoting Wang and Prof. Yu-Fei Song

      Version of Record online: 16 JAN 2014 | DOI: 10.1002/chem.201303933

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      Polymerizing POMs: A new photosensitive polyoxometalate (POM) organic–inorganic hybrid compound has been prepared by covalently tethering coumarin moieties onto a Mn–Anderson cluster. This compound has been fully characterized by 1H NMR, 13C NMR, FTIR, and UV/Vis spectroscopy, and ESI-MS. This compound can undergo reversible light-driven polymerization (see scheme) and this process has been characterized in detail.

    4. Organic Synthesis

      Ruthenium(II)/Chiral Brønsted Acid Co-Catalyzed Enantioselective Four-Component Reaction/Cascade Aza-Michael Addition for Efficient Construction of 1,3,4-Tetrasubstituted Tetrahydroisoquinolines (pages 1505–1509)

      Dr. Jun Jiang, Xiaochu Ma, Dr. Changge Ji, Dr. Zhenqiu Guo, Taoda Shi, Dr. Shunying Liu and Prof. Wenhao Hu

      Version of Record online: 16 JAN 2014 | DOI: 10.1002/chem.201304576

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      An elegant synergistic catalytic system comprising a ruthenium complex with a chiral Brønsted acid was developed for a four-component Mannich/cascade aza-Michael reaction. The transformation features a mild, rapid, and efficient method for the synthesis of enantiomerically pure 1,3,4-tetrasubstituted tetrahydroquinolines from simple starting precursors in moderate yields with high diastereo- and enantioselectivity (see scheme, Cbz=carbobenzyloxy).

    5. Catalysis

      Enzyme Design from the Bottom Up: An Active Nickel Electrocatalyst with a Structured Peptide Outer Coordination Sphere (pages 1510–1514)

      Dr. Matthew L. Reback, Dr. Garry W. Buchko, Dr. Brandon L. Kier, Bojana Ginovska-Pangovska, Dr. Yijia Xiong, Dr. Sheri Lense, Dr. Jianbo Hou, Dr. John A. S. Roberts, Dr. Christina M. Sorensen, Dr. Simone Raugei, Dr. Thomas C. Squier and Dr. Wendy J. Shaw

      Version of Record online: 17 JAN 2014 | DOI: 10.1002/chem.201303976

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      A H2 production catalyst with a peptide-based, structured outer coordination sphere has been synthesized (see figure), making it possible to evaluate the effect of the outer coordination sphere on molecular catalysts. The resulting complex, [Ni(PPh2NAPPA-WR10)2]2+, retains the secondary structure of the peptide (WR10) and is active for H2 production, with enhanced rates compared with the parent complex [Ni(PPh2NAPPA)2]2+ (APPA=4-aminophenyl propionic acid).

    6. Magnetic Nanoparticles

      Phenylene-Coated Magnetic Nanoparticles that Boost Aqueous Asymmetric Transfer Hydrogenation Reactions (pages 1515–1519)

      Dr. Xiaoshuang Gao, Rui Liu, Dacheng Zhang, Meng Wu, Tanyu Cheng and Prof. Guohua Liu

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201302797

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      Magnetic moments: Phenylene-coated organorhodium-functionalized magnetic nanoparticles (NPs) are developed through co-condensation of chiral 4-(trimethoxysilyl)ethyl)phenylsulfonyl-1,2-diphenylethylene-diamine and 1,4-bis(triethyoxysilyl)benzene onto Fe3O4 followed by complexation with [{Cp*RhCl2}2]. The magnetic NPs exhibit excellent catalytic activity and high enantioselectivity in asymmetric transfer hydrogenation in water, owing to high hydrophobicity and the confined chiral organorhodium, and can be easily recovered with an external magnet and reused.

    7. Catalytic Allylation

      Mechanistic Insights into the Pd-Catalyzed Direct Amination of Allyl Alcohols: Evidence for an Outer-Sphere Mechanism Involving a Palladium Hydride Intermediate (pages 1520–1524)

      Supaporn Sawadjoon, Dr. Per J. R. Sjöberg, Dr. Andreas Orthaber, Prof. Olle Matsson and Dr. Joseph S. M. Samec

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201303431

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      Two cleavages: The mechanism of the direct amination of allyl alcohol by palladium complexes bearing triphenylphosphite ligands has been explored. Kinetic isotope and ESI-MS studies are in good agreement with that both O[BOND]H bond and C[BOND]O bond cleavages are involved in rate-determining steps. Furthermore, stereochemical studies support an outer-sphere nucleophilic attack of the π-allylpalladium intermediate.

    8. Twisted Aromatics

      Hexaazatrinaphthylenes with Different Twists (pages 1525–1528)

      Sunil Choudhary, Cristian Gozalvez, Alexander Higelin, Prof. Ingo Krossing, Prof. Manuel Melle-Franco and Prof. Aurelio Mateo-Alonso

      Version of Record online: 9 DEC 2013 | DOI: 10.1002/chem.201304071

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      Let′s do the twist: A synthetic strategy that allows the induction of twist angles of different sizes in 5,6,11,12,17,18-hexaazatrinaphthylene (HATNA) chromophores is reported (see figure). The different twist angles are accompanied by measurable changes in the emission and electrochemical characteristics of HATNA.

  7. Full Papers

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

      Encapsulation of a Catalytic Imidazolium Salt into Avidin: Towards the Development of a Biohybrid Catalyst Active in Ionic Liquids (pages 1530–1538)

      Vincent Gauchot, Dr. Mathieu Branca and Prof. Dr. Andreea Schmitzer

      Version of Record online: 2 JAN 2014 | DOI: 10.1002/chem.201303865

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      Biohybrid catalysts capable of catalyzing the aldol reaction are prepared from avidin and biotinylated imidazolium salts with either racemic or enantiomerically pure catalytic anions. Supramolecular encapsulation (see figure) of the biotinylated catalyst in avidin resulted in good selectivities for the aldol reaction when performed in ionic liquid/water mixtures and the adaptive and cooperative positioning of the anionic catalyst inside the avidin protein is discussed.

    2. Palladium Catalysis

      Dormant versus Evolving Aminopalladated Intermediates: Toward a Unified Mechanistic Scenario in PdII-Catalyzed Aminations (pages 1539–1546)

      Dr. Jamshid Rajabi, Mélanie M. Lorion, Vu Linh Ly, Dr. Frédéric Liron, Dr. Julie Oble, Prof. Dr. Guillaume Prestat and Prof. Dr. Giovanni Poli

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201302744

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      Asleep or awake? Unsaturated N nucleophiles react through two competing pathways under PdII catalysis: C[BOND]H allylic activation and aminopalladation. New data are in accord with the initial generation of a high-energy cyclic aminopalladated intermediate (API) that can either evolve along different pathways such as β-H elimination, oxidation, or carbopalladation, or lay dormant, the latter leading to alternative types of reactivity, such as allylic C[BOND]H activation or [3,3]-sigmatropic rearrangement, gaining the upper hand (see scheme; Ts=p-toluenesulfonyl).

    3. Foldamers

      Tuning the Guest-Binding Ability of a Helically Folded Capsule by In Situ Modification of the Aromatic Oligoamide Backbone (pages 1547–1553)

      Dr. Guillaume Lautrette, Dr. Christophe Aube, Dr. Yann Ferrand, Dr. Muriel Pipelier, Dr. Virginie Blot, Dr. Christine Thobie, Dr. Brice Kauffmann, Prof. Didier Dubreuil and Dr. Ivan Huc

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201303929

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      Controlled release: Altering the shape of a foldamer-based helical receptor at a specific location changes the binding properties and may thus trigger guest release. To target one heterocycle among many others along the helix backbone, the selective four-electron ring contraction of pyridazine into pyrrole was used (see figure).

    4. Metal–Organic Frameworks

      Porous MII/Pyrimidine-4,6-Dicarboxylato Neutral Frameworks: Synthetic Influence on the Adsorption Capacity and Evaluation of CO2-Adsorbent Interactions (pages 1554–1568)

      Dr. Javier Cepeda, Dr. Sonia Pérez-Yáñez, Dr. Garikoitz Beobide, Dr. Oscar Castillo, Dr. Michael Fischer, Prof. Antonio Luque and Prof. Paul A. Wright

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201303627

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      MOF–CO2 interactions: The procedure employed for the synthesis of a new family of metal–organic frameworks (MOFs) has allowed the optimisation of their crystallinity and adsorption capacity (see figure). The solvent-free method provides the opportunity to prepare heterometallic compounds, in addition to rendering the adsorbents with the highest performance. The experimental CO2 adsorption behaviour is discussed and supported by quantum-mechanical calculations involving the CO2 interactions with the adsorbent surface.

    5. Single-Ion Magnets

      Unraveling the Crystal Structure of Lanthanide–Murexide Complexes: Use of an Ancient Complexometry Indicator as a Near-Infrared-Emitting Single-Ion Magnet (pages 1569–1576)

      Xiaohui Yi, Dr. Kevin Bernot, Vincent Le Corre, Dr. Guillaume Calvez, Dr. Fabrice Pointillart, Dr. Olivier Cador, Dr.  Boris Le Guennic, Julie Jung, Dr. Olivier Maury, Dr. Virginie Placide, Dr. Yannick Guyot, Dr. Thierry Roisnel, Dr. Carole Daiguebonne and Prof. Olivier Guillou

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201303833

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      Structural evidence of the complexation color-change of murexide solutions in the presence of a lanthanide is provided. The [Yb(Murex)3]11 H2O derivative possessing a N3O6 tricapped square-antiprism environment shows single-ion magnet (SIM) behavior (see figure). Magnetic and photophysical properties can be correlated. Participation of excited Stark sub-levels of the 2F5/2 excited state to near infrared (NIR) emission is evidenced.

    6. Photochemistry

      Strongly Luminous Tetranuclear Gold(I) Complexes Supported by Tetraphosphine Ligands, meso- or rac-Bis[(diphenylphosphinomethyl)phenylphosphino]methane (pages 1577–1596)

      Prof. Tomoaki Tanase, Risa Otaki, Tomoko Nishida, Hiroe Takenaka, Dr. Yukie Takemura, Prof. Bunsho Kure, Prof. Takayuki Nakajima, Prof. Yasutaka Kitagawa and Prof. Taro Tsubomura

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201303729

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      Go for gold: A series of AuI4 complexes with new tetraphosphine ligands, meso- and rac-bis[(diphenylphosphinomethyl)phenylphosphino]methane (meso- and rac-dpmppm) were synthesized to demonstrate that the tetranuclear AuI alignment varies depending on syn and anti arrangements of the two dpmppm ligands as bent, linear, and zigzag structures (see scheme).

    7. Hybrid Materials

      Towards Eumelanin@Zeolite Hybrids: Pore-Size-Controlled 5,6-Dihydroxyindole Polymerization (pages 1597–1601)

      Dr. Eko Adi Prasetyanto, Dr. Paola Manini, Prof. Alessandra Napolitano, Prof. Orlando Crescenzi, Prof. Marco d'Ischia and Prof. Luisa De Cola

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201303682

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      Confinement in nanometer-sized channels of zeolite L allowed the formation and stabilization of the quinonoid 5,6-dihydroxyindole dimer(s) as a precursor step to synthetic eumelanin-like polymers. The entrapped species were characterized by an integrated spectroscopic and computational approach. In mesoporous silica, the larger diameter of the channels determines the formation of black eumelanin-type materials.

    8. Enzymes

      New Insights into the Nature of Observable Reaction Intermediates in Cytochrome P450 NO Reductase by Using a Combination of Spectroscopy and Quantum Mechanics/Molecular Mechanics Calculations (pages 1602–1614)

      Dr. Christoph Riplinger, Dr. Eckhard Bill, Prof. Dr. Andreas Daiber, Prof. Dr. Volker Ullrich, Prof. Dr. Hirofumi Shoun and Prof. Dr. Frank Neese

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/chem.201302443

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      New insights: A detailed experimental and theoretical spectroscopic characterization of the reaction intermediates of cytochrome P450 NO reductase gives insight into the reaction mechanism (see figure). The intermediacy of two FeIII species is in agreement with the experimental data.

    9. Heterometallic Complexes

      Synthesis of Heterodinuclear Hemisalen Complexes on a Hexaarylbenzene Scaffold and their Application for the Cross-Pinacol Coupling Reaction (pages 1615–1621)

      Akihiro Miyasaka, Dr. Toru Amaya and Prof. Toshikazu Hirao

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201303946

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      Working together: Dihemisalen ligands on a hexaaryl benzene scaffold were designed and the heterodinuclear complexes 1cis with vanadium(V) and titanium(IV) were synthesized from the corresponding disalicylaldehyde compound (see scheme). By using the heterodinuclear catalysts, the selective intermolecular cross-pinacol coupling reaction between aliphatic and aromatic aldehydes is demonstrated.

    10. N-Heterocyclic Carbene Solvation

      How Can a Carbene be Active in an Ionic Liquid? (pages 1622–1629)

      Martin Thomas, Martin Brehm, Dr. Oldamur Hollóczki and Prof. Dr. Barbara Kirchner

      Version of Record online: 27 DEC 2013 | DOI: 10.1002/chem.201303329

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      The methyl group in the game: When an N-heterocyclic carbene is dissolved in an imidazole-based ionic liquid, it cannot form hydrogen bonds with the ring hydrogen atoms of the cation if basic anions are present; therefore, it binds to a methyl group instead (see figure). The lack of strong hydrogen bonding keeps the carbene available for reactions.

    11. Substituent Effects

      Synergistic Effects of Lewis Bases and Substituents on the Electronic Structure and Reactivity of Boryl Radicals (pages 1630–1637)

      Dr. Dongmei Lu, Dr. Chao Wu and Dr. Pengfei Li

      Version of Record online: 16 JAN 2014 | DOI: 10.1002/chem.201303705

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      Synergistic effects of substituents and Lewis bases on the reactivity of boryl radicals with various topologies are examined (see figure). Two electron-donating substituents in combination with a good σ-donating and π-accepting Lewis base stabilize boryl radicals much more efficiently than if only substituents or Lewis bases are used.

    12. Nanotubes

      Polytwistane (pages 1638–1645)

      Shiblee R. Barua, Henrik Quanz, M. Sc. Martin Olbrich, Prof. Dr. Peter R. Schreiner, Prof. Dr. Dirk Trauner and Prof. Dr. Wesley D. Allen

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201303081

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      Let's do the twist: Polytwistane is an experimentally unrealized (CH)n alkane exhibiting helical chirality and a regular carbon nanotube. A rigorous theoretical analysis of its topology reveals that polytwistane contains a non-repeating, alternating primary helix stiffened by longitudinal crosslinks (see figure). Thermochemical computations suggest that polytwistane is a viable synthetic target.

    13. Cage Compounds

      Hydrogen-Bond-Driven Controlled Molecular Marriage in Covalent Cages (pages 1646–1657)

      Koushik Acharyya and Prof. Dr. Partha Sarathi Mukherjee

      Version of Record online: 30 DEC 2013 | DOI: 10.1002/chem.201303397

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      Marriage guidance: Controlled self-sorting in covalent cage formation, including cage-to-cage transformation, has been achieved by using hydrogen bonding as a driving force (see figure). Unconventional imine bond metathesis in organic cages is also reported.

    14. Host–Guest Systems

      Host–Guest Chemistry of Aromatic-Amide-Linked Bis- and Tris-Calix[4]pyrroles with Bis-Carboxylates and Citrate Anion (pages 1658–1668)

      Dr. Grazia Cafeo, Dr. Giuseppe Gattuso, Prof. Franz H. Kohnke, Dr. Georgia Papanikolaou, Dr. Aldo Profumo and Dr. Camillo Rosano

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201303265

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      Calixpyrrole receptors: Compounds 1 a and 1 b with p- or m-phthaloyl or trimesic chloride have been used to prepare bis-and tris-calixpyrrole receptors (see figure). The polytopic receptors were tested as ligands of various bis-carboxylates and citrate (see structure on the right). The binding modes in the complexes were explored and depend on the stereochemical match between the host and guest.

    15. Single-Molecule Magnets

      Insertion of a Single-Molecule Magnet inside a Ferromagnetic Lattice Based on a 3D Bimetallic Oxalate Network: Towards Molecular Analogues of Permanent Magnets (pages 1669–1676)

      Dr. Miguel Clemente-León, Prof. Eugenio Coronado, Prof. Carlos J. Gómez-García, Dr. Maurici López-Jordà, Dr. Agustín Camón, Ana Repollés and Dr. Fernando Luis

      Version of Record online: 10 DEC 2013 | DOI: 10.1002/chem.201303044

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      Magnetic couple: The insertion of a single-molecule magnet (SMM) into a ferromagnetic bimetallic oxalate network affords the hybrid compound [MnIII(salen)(H2O)]2[MnIICrIII(ox)3]2(MeOH)3(H2O). The interaction between the two magnetic networks leads to the antiparallel arrangement of their respective magnetizations (see figure). This coupling induces a large magnetization hysteresis below 1 K, in sharp contrast with the near-reversible magnetizations that the SMMs and the oxalate ferromagnetic lattice show under the same conditions.

    16. Enzyme Models

      Synthesis and Reactivity of Mononuclear Iron Models of [Fe]-Hydrogenase that Contain an Acylmethylpyridinol Ligand (pages 1677–1682)

      Dr. Bowen Hu, Prof. Dr. Dafa Chen and Prof. Dr. Xile Hu

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201304290

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      Swinging a five iron: A series of five-coordinate thiolate iron complexes that precisely model the active site of [Fe]-hydrogenase have been synthesized (see figure; cys=cysteine). These complexes are first mononuclear models with an acylmethylpyridinol ligand.

    17. Polyoxometalates

      Evolution of Actinyl Peroxide Clusters U28 in Dilute Electrolyte Solution: Exploring the Transition from Simple Ions to Macroionic Assemblies (pages 1683–1690)

      Dr. Dong Li, Silas Simotwo, Prof. Dr. May Nyman and Prof. Dr. Tianbo Liu

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201303266

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      Two generations of capsules: Two actinyl peroxide U28 clusters (see figure) show interesting self-assembly behavior in dilute electrolyte solutions. This transition from simple ions to macroionic assemblies can be regulated by, for example, counterion type, counterion concentration, and temperature.

    18. Synthetic Methods

      Catalytic, Asymmetric Synthesis of Phosphonic γ-(Hydroxyalkyl)butenolides with Contiguous Quaternary and Tertiary Stereogenic Centers (pages 1691–1700)

      Marcus Frings, Dr. Isabelle Thomé, Dr. Ingo Schiffers, Dr. Fangfang Pan and Prof. Dr. Carsten Bolm

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201304331

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      Best of two worlds: A chiral copper-sulfoximine catalyst unites biologically relevant α-hydroxy phosphonates and γ-(hydroxyalkyl) butenolides into one structural motif with regio-, diastereo- and enantioselectivity up to the limits of detection (see scheme; Tf=trifluoromethanesulfonyl, TMS=trimethylsilyl).

    19. Catalysis

      Oxidation of Benzyl Alcohol and Carbon Monoxide Using Gold Nanoparticles Supported on MnO2 Nanowire Microspheres (pages 1701–1710)

      Dr. Mosaed Alhumaimess, Dr. Zhongjie Lin, Dr. Qian He, Dr. Li Lu, Dr. Nickolaos Dimitratos, Dr. Nicholas F. Dummer, Dr. Marco Conte, Dr. Stuart H. Taylor, Dr. Jonathan K. Bartley, Prof. Christopher J. Kiely and Prof. Graham J. Hutchings

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201303355

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      Shape selectivity: Different nanostructured MnO2 materials were prepared by adjusting the synthesis conditions. When used as a support for gold oxidation catalysts, it was found that α-MnO2 spherical agglomerates performed the best in the liquid phase oxidation of benzyl alcohol, whereas β-MnO2 nanowires performed better for gas-phase CO oxidation (see figure).

    20. Domino Reactions

      FeCl3-Mediated Three-Component Cascade Reaction: An Effective Approach to the Construction of Highly Functionalized Pyrrolo[1,2-c]quinazolinones (pages 1711–1719)

      Hu-Fei Zheng, Dr. Zhi-Hua Yu, Wei Yuan, Prof. Dr. Zi-Long Tang, John Clough, Yu-Cheng Gu and Prof. Dr. De-Qing Shi

      Version of Record online: 30 DEC 2013 | DOI: 10.1002/chem.201304028

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      An iron trigger: An FeCl3-triggered three-component domino strategy enables access to highly functionalized pyrrolo[1,2-c]quinazolinones in a single step (see scheme, MS=molecular sieves). The obtained products can be used as building blocks in the synthesis of diverse, potentially biologically active nitrogen-containing heterocycles. This method features mild conditions, a simple work-up, as well as a wide substrate scope.

    21. Corrole Tautomerism

      Insights into the Tautomerism in meso-Substituted Corroles: A Variable-Temperature 1H, 13C, 15N, and 19F NMR Spectroscopy Study (pages 1720–1730)

      Prof. Sławomir Szymański, Piotr Paluch, Prof. Daniel T. Gryko, Dr. Agnieszka Nowak-Król, Dr. Wojciech Bocian, Jerzy Sitkowski, Beata Koszarna, Justyna Śniechowska, Prof. Marek J. Potrzebowski and Prof. Lech Kozerski

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/chem.201303406

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      The NH proton dynamics inside the interior of a corrole macrocycle have been investigated in detail by consideration of variable-temperature NMR spectra of tris(pentafluorophenyl)corrole (see scheme), measured for two different concentrations of the compound in toluene. Intra- and intermolecular mechanisms of the proton-exchange processes have been identified.

    22. Organic Synthesis

      Phosphine-Catalyzed [3+2] Cycloaddition Reactions of Azomethine Imines with Electron-Deficient Alkenes: A Facile Access to Dinitrogen-Fused Heterocycles (pages 1731–1736)

      Zhen Li, Hao Yu, Honglei Liu, Lei Zhang, Hui Jiang, Bo Wang and Prof. Dr. Hongchao Guo

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201303625

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      Simplicity is best: Phosphine-catalyzed [3+2] cycloaddition of azomethine imines and phenylsulfonyl alkenes was accomplished. The reactions are operationally simple and proceed smoothly under mild reaction conditions, affording various 1,2-dinitrogen-containing heterocycles in moderate to excellent yields (see scheme).

    23. Supramolecular Chemistry

      Light-Controlled Formation of Vesicles and Supramolecular Organogels by a Cholesterol-Bearing Amphiphilic Molecular Switch (pages 1737–1742)

      Jochem T. van Herpt, Dr. Jetsuda Areephong, Dr. Marc C. A. Stuart, Prof. Dr. Wesley R. Browne and Prof. Dr. Ben L. Feringa

      Version of Record online: 16 JAN 2014 | DOI: 10.1002/chem.201302902

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      A state of light and medium: A unique single-molecule system has been designed that shows responsive self-assembly in both water and organic solvents (see scheme). Light-triggered reversible vesicle formation in aqueous solutions is reported. The cholesterol-bearing amphiphilic dithienylethene molecule shows a different behavior in organic media, in which light-controlled organogel formation is observed. The aggregation behavior of this molecule in different media is described, which opens new avenues in responsive soft materials.

    24. Heterogeneous Catalysis

      The Effect of Grafting Zirconia and Ceria onto Alumina as a Support for Silicotungstic Acid for the Catalytic Dehydration of Glycerol to Acrolein (pages 1743–1752)

      Dr. Muhammad H. Haider, Dr. Carmine D'Agostino, Dr. Nicholas F. Dummer, Dr. Mick D. Mantle, Prof. Lynn F. Gladden, Prof. David W. Knight, Dr. David J. Willock, Dr. David J. Morgan, Prof. Stuart H. Taylor and Prof. Graham J. Hutchings

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/chem.201302348

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      Grafting zirconia onto δ,θ-alumina as a support for silicotungstic acid (STA) improves the catalytic performance for glycerol dehydration to acrolein. PFG-NMR diffusion studies show that catalyst stability is related to pore structure stability, and that grafting leads to decreased acid strength, more tortuous pore structure, and a decrease in coke formation.

    25. Nanostructures

      Pt3Co Concave Nanocubes: Synthesis, Formation Understanding, and Enhanced Catalytic Activity toward Hydrogenation of Styrene (pages 1753–1759)

      Chenyu Wang, Dr. Cuikun Lin, Dr. Lihua Zhang, Dr. Zewei Quan, Dr. Kai Sun, Dr. Bo Zhao, Dr. Feng Wang, Nathan Porter, Dr. Yuxuan Wang and Prof. Dr. Jiye Fang

      Version of Record online: 30 DEC 2013 | DOI: 10.1002/chem.201301724

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      Anisotropic overgrowth: Pt3Co concave nanocubes bounded by high-index facets were prepared with a facile wet-chemical method. The formation process for such concave nanostructures was systematically studied, and a plausible mechanism was proposed. These nanocrystals can be used as advanced nanocatalysts, showing high activity and reusability toward hydrogenation of styrene (see figure).

    26. DNA

      Structural and Magnetic Properties of a Variety of Transition Metal Incorporated DNA Double Helices (pages 1760–1764)

      Pralok K. Samanta and Prof. Swapan K. Pati

      Version of Record online: 30 DEC 2013 | DOI: 10.1002/chem.201302628

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      Base metal: Magnetic exchange interactions are studied for a variety of transition metals (M=Mn, Fe, Co, Ni, and Cu) inside metal–DNA (M–DNA) double helices, modified with either hydroxypyridone (H) or bis(salicylaldehyde)ethylenediamine (S–en) metalated base pairs (see figure). Ferromagnetic and antiferromagnetic interactions can be tuned by varying the transition metal ions and the number of metal ions.

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