Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 3

January 14, 2013

Volume 52, Issue 3

Pages 773–1053

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: Heterolytic Activation of H2 Using a Mechanically Interlocked Molecule as a Frustrated Lewis Base (Angew. Chem. Int. Ed. 3/2013) (page 773)

      Christopher B. Caputo, Dr. Kelong Zhu, V. Nicholas Vukotic, Prof. Stephen J. Loeb and Prof. Douglas W. Stephan

      Version of Record online: 11 DEC 2012 | DOI: 10.1002/anie.201209490

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      The reactivity of frustrated Lewis pairs is induced by the utilization of a sterically unencumbered aniline as the axle in a [2]rotaxane. In their Communication on page 960 ff., S. J. Loeb, D. W. Stephan, and co-workers show that the [2]rotaxane imparts enough steric bulk to the base to preclude adduct formation with B(C6F5)3. This unique modification also shows frustrated Lewis pair reactivity in the activation of H2 at room temperature.

    2. You have free access to this content
      Inside Cover: Electrical Switching Behavior of a [60]Fullerene-Based Molecular Wire Encapsulated in a Syndiotactic Poly(methyl methacrylate) Helical Cavity (Angew. Chem. Int. Ed. 3/2013) (page 774)

      Dr. Shengli Qi, Dr. Hiroki Iida, Dr. Lili Liu, Prof. Stephan Irle, Prof. Wenping Hu and Prof. Eiji Yashima

      Version of Record online: 12 DEC 2012 | DOI: 10.1002/anie.201209492

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      A helical syndiotactic poly(methyl methacrylate) (st-PMMA) encapsulates C60 molecules within its helical cavity to form a supramolecular peapod-like molecular wire. In their Communication on page 1049 ff., S. Qi, S. Irle, E. Yashima, and co-workers report that sandwich devices fabricated using this helical st-PMMA/C60 inclusion complex exhibit an irreversible electrical switching effect, which results from a violent Coulomb explosion in the peapod C60 wires during the charge injection process.

    3. You have free access to this content
      Inside Back Cover: Light-Triggered Sequence-Specific Cargo Release from DNA Block Copolymer–Lipid Vesicles (Angew. Chem. Int. Ed. 3/2013) (page 1055)

      Dr. Alberto Rodríguez-Pulido, Alina I. Kondrachuk, Dr. Deepak K. Prusty, Jia Gao, Prof. Dr. Maria A. Loi and Prof. Dr. Andreas Herrmann

      Version of Record online: 10 JAN 2013 | DOI: 10.1002/anie.201209861

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      Sequence-specific cargo release from DNA-encoded lipid vesicles through the stable tagging of a liposome surface with amphiphilic DNA block copolymers (DBCs) is reported by A. Herrmann and co-workers in their Communication on page 1008 ff. Hybridization of anchored DBCs with an oligonucleotide photosensitizer is the key to light-induced singlet oxygen generation close to the lipid membrane, which results in the oxidation of polymer anchors and/or unsaturated phospholipids, leading to release of the vesicle payload.

    4. You have free access to this content
      Back Cover: Metabolomics Enables the Structure Elucidation of a Diatom Sex Pheromone (Angew. Chem. Int. Ed. 3/2013) (page 1056)

      Dr. Jeroen Gillard, Johannes Frenkel, Valerie Devos, Prof. Dr. Koen Sabbe, Carsten Paul, Dr. Martin Rempt, Prof. Dr. Dirk Inzé, Prof. Dr. Georg Pohnert, Prof. Dr. Marnik Vuylsteke and Prof. Dr. Wim Vyverman

      Version of Record online: 2 JAN 2013 | DOI: 10.1002/anie.201209860

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      Asexual division of the diatom Seminavis robusta (see picture) results in size reduction owing to the restriction of the biomineralized cell wall. Below a critical size, diatoms must find a suitable partner for mating and sexual reproduction. In their Communication on page 854 ff., G. Pohnert et al. describe metabolomic studies in which L-diproline was identified as the first diatom pheromone.

  2. Editorial

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. You have free access to this content
      The Catalyst Genome (pages 776–777)

      Prof. Jens K. Nørskov and Dr. Thomas Bligaard

      Version of Record online: 4 DEC 2012 | DOI: 10.1002/anie.201208487

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      “… The quest for the materials genome—the properties of a material that define its functional properties—has started. This signifies a transition to a new era of materials research where large amounts of materials data become available. The expectation is that this will significantly speed up the discovery of new materials …” Read more in the Editorial by J. K. Nørskov and T. Bligaard.

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
  4. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
  5. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Achim Müller (pages 800–802)

      Version of Record online: 2 JAN 2013 | DOI: 10.1002/anie.201209135

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      “I like refereeing because I can help to improve the quality of science. My favorite place on earth is somewhere in the mountains …” This and more about Achim Müller can be found on page 800.

  6. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
  7. Book Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
  8. Highlights

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. E-Alkenes

      Catalytic Stereoselective Semihydrogenation of Alkynes to E-Alkenes (pages 806–808)

      Iacovos N. Michaelides and Prof. Dr. Darren J. Dixon

      Version of Record online: 17 DEC 2012 | DOI: 10.1002/anie.201208120

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      Less is more: Significant advancements have been made in recent years in the development of the E-selective, catalytic, functional-group-tolerant semihydrogenation of alkynes to E-alkenes through transition-metal catalysis (see scheme). For this type of catalysis, the use of mononuclear metal catalysts is superior to that of multinuclear metal catalysts.

    2. Asymmetric Synthesis

      Enantioselective Synthesis of Carbocycles and Heterocycles by Radical/Polar and Polar/Radical Cascades (pages 809–811)

      Dr. Shovan Mondal, Prof. Dr. Michèle P. Bertrand and Dr. Malek Nechab

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/anie.201207518

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      Radically efficient: New and appealing enantioselective cyclizations leading to highly functionalized carbocycles and heterocycles have been reported (see scheme; TMS=trimethylsilyl). These methodologies, based on the cascade combination of radical and polar steps, provide alternatives to conventional methodologies.

  9. Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Photocatalysis with Visible Light

      Semiconductor Photocatalysis—Mechanistic and Synthetic Aspects (pages 812–847)

      Prof. Dr. Horst Kisch

      Version of Record online: 4 DEC 2012 | DOI: 10.1002/anie.201201200

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      Photoinduced charge generation at semiconductor surfaces is currently the most promising method for the chemical utilization of visible light. These charges can be utilized for catalytic redox processes such as nitrogen fixation, functionalization of alkanes, and linear addition reactions of olefins to 1,2-diazenes and imines. Semiconductor photocatalysis combines aspects of classical photochemistry with electrochemistry, solid-state chemistry, and heterogeneous catalysis.

  10. Communications

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Light-Triggered Chemical Biology

      Control of Nanomolar Interaction and In Situ Assembly of Proteins in Four Dimensions by Light (pages 848–853)

      Noemi Labòria, Dr. Ralph Wieneke and Prof. Robert Tampé

      Version of Record online: 2 JAN 2013 | DOI: 10.1002/anie.201206698

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      Making light work: Photoactivatable multivalent trisNTA compounds have been developed for the in situ labeling and assembly of His-tagged proteins in time and space (see picture). This small light-tunable lock-and-key system offers the opportunity to trigger nanomolar protein interactions, such as receptor clustering, or biotechnological applications, for example, multiprotein arrays.

    2. Pheromones

      Metabolomics Enables the Structure Elucidation of a Diatom Sex Pheromone (pages 854–857)

      Dr. Jeroen Gillard, Johannes Frenkel, Valerie Devos, Prof. Dr. Koen Sabbe, Carsten Paul, Dr. Martin Rempt, Prof. Dr. Dirk Inzé, Prof. Dr. Georg Pohnert, Prof. Dr. Marnik Vuylsteke and Prof. Dr. Wim Vyverman

      Version of Record online: 12 DEC 2012 | DOI: 10.1002/anie.201208175

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      Finding a mate: Diatoms use chemical signals to sense the presence of and find their mating partners. When the metabolic profiles of sexually active and inactive cells were compared, a highly up-regulated metabolite generated in the attracting mating type was identified as di-L-prolyl diketopiperazine, the first diatom pheromone.

    3. Complexes of Yellow Arsenic

      Intact As4 Tetrahedra Coordinated Side-On to Metal Cations (pages 858–861)

      Dipl.-Chem. Christoph Schwarzmaier, Prof. Dr. Marek Sierka and Prof. Dr. Manfred Scheer

      Version of Record online: 4 DEC 2012 | DOI: 10.1002/anie.201208226

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      Extremely light sensitive yellow arsenic (As4) reacts with a weakly coordinated silver cation to afford [Ag(η2-As4)2]+ [Al{OC(CF3)3}4] as the first known homoleptic arsenic complex. DFT calculations and Raman spectroscopy clearly indicate the coordination of two intact As4 tetrahedra. This unprecedented complex is used as an As4 transfer agent, which is demonstrated by the synthesis of [(PPh3)Au(η2-As4)]+[Al{OC(CF3)3}4].

    4. Structure and Bonding

      CuTe: Remarkable Bonding Features as a Consequence of a Charge Density Wave (pages 862–865)

      Karoline Stolze, Dr. Anna Isaeva, Fabian Nitsche, Dr. Ulrich Burkhardt, Prof. Dr. Hannes Lichte, Dr. Daniel Wolf and Prof. Dr. Thomas Doert

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/anie.201207333

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      CuTe bonds! A delicate balance between polyanionic Te[BOND]Te bonds and multicenter Cu[BOND]Cu and Cu[BOND]Te interactions is found in the modulated structure of CuTe. Modulated CuTe is thus an alliance of typical bonding properties of polyanionic and metal-rich compounds.

    5. Diphenol Synthesis

      The Acetal Concept: Regioselective Access to ortho,ortho-Diphenols via Dibenzo-1,3-dioxepines (pages 866–869)

      Dr. Kye-Simeon Masters and Prof. Dr. Stefan Bräse

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/anie.201207485

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      Traditional methods are ill-suited for the synthesis of ortho,ortho-biphenols, a structural motif found in many polyphenolic natural products, as well as synthetically useful compounds such as the chiral ligands binol, vapol, and vanol. The new route consists of a radical-based reaction of an acetal-tethered biphenyl ether substrate and subsequent hydrolytic cleavage of the dibenzo-1,3-dioxepine intermediate.

    6. Copper Peroxido Complexes

      Characterization of a Macrocyclic end-on Peroxido Copper Complex (pages 870–873)

      Tobias Hoppe, Stefan Schaub, Jonathan Becker, Dr. Christian Würtele and Prof. Dr. Siegfried Schindler

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/anie.201205663

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      Thirty years on: The dinuclear copper peroxido complex [(tet b)CuO2Cu(tet b)]2+ has been structurally characterized (see picture: Cu yellow, O red, N pink; tet b=rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). This complex is quite persistent in solution at room temperature and is the first example of a structurally characterized copper dioxygen adduct complex with a macrocyclic ligand based on earlier studies by Valentine et al.

    7. Gold(III) Alkene Complexes

      Gold(III) Olefin Complexes (pages 874–877)

      Dr. Nicky Savjani, Dragoş-Adrian Roşca, Dr. Mark Schormann and Prof. Dr. Manfred Bochmann

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/anie.201208356

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      Zeise's salt gets company: 185 years after the report of the well-known platinum(II) ethylene compound, examples of isolable olefin complexes of its isoelectronic neighbor in the periodic table, gold(III), have been prepared (see picture). The complexes are very susceptible towards nucleophilic attack; there is also structural evidence for AuIII–Ag interactions.

    8. Asymmetric Catalysis

      Palladium/Chiral Amine Co-catalyzed Enantioselective β-Arylation of α,β-Unsaturated Aldehydes (pages 878–882)

      Prof. Dr. Ismail Ibrahem, Dr. Guangning Ma, Samson Afewerki and Prof. Dr. Armando Córdova

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/anie.201208634

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      Palladium and a simple chiral amine are used as co-catalysts for the enantioselective conjugate addition of aryl boronic acids to α,β-unsaturated aldehydes (see scheme). The synthetic utility of this co-catalyzed reaction was demonstrated in the short total syntheses of (R)-(−)-curcumene and 4-aryl-2-ones.

    9. C[BOND]C Activation

      Highly Chemoselective Carbon[BOND]Carbon σ-Bond Activation: Nickel/Lewis Acid Catalyzed Polyfluoroarylcyanation of Alkynes (pages 883–887)

      Dr. Yasunori Minami, Hirofumi Yoshiyasu, Dr. Yoshiaki Nakao and Prof. Dr. Tamejiro Hiyama

      Version of Record online: 20 NOV 2012 | DOI: 10.1002/anie.201207880

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      Selective C[BOND]C bond cleavage: A catalyst consisting of nickel(0)/DPEphos and BPh3 is highly effective for the addition of polyfluorobenzonitriles to alkynes through selective activation of the C[BOND]CN bond over the C[BOND]H or C[BOND]F bonds. The addition reaction is applicable to the sequential insertion of two different alkynes into C[BOND]CN and C[BOND]H bonds (see scheme).

    10. Methane Activation

      Vacuum Ultraviolet Photoionization Studies of PtCH2 and H-Pt-CH3: A Potential Energy Surface for the Pt+CH4 Reaction (pages 888–891)

      Prof. Manori Perera, Prof. Ricardo B. Metz, Dr. Oleg Kostko and Dr. Musahid Ahmed

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/anie.201207931

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      Does Charge Matter? Direct vacuum UV measurement of ionization energies reveals that C–H insertion by Pt to form H-Pt-CH3 is highly exoergic, while production of PtCH2+H2 is slightly endoergic. Experiments and spin-orbit DFT calculations reveal surprisingly similar energetics for dehydrogenation of methane by neutral and cationic platinum. Red lines in the picture indicate experimentally determined energies.

    11. Indole Functionalization

      Regio- and Stereoselective Allylation and Crotylation of Indoles at C2 Through the Use of Potassium Organotrifluoroborate Salts (pages 892–895)

      Dr. Farhad Nowrouzi and Prof. Dr. Robert A. Batey

      Version of Record online: 6 DEC 2012 | DOI: 10.1002/anie.201207978

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      A practical method for the allylation, prenylation, propargylation, and diastereoselective crotylation of indoles has been developed using air- and moisture-stable potassium organotrifluoroborate reagents (see scheme). Lewis acids such as BF3⋅Et2O promote addition to afford 2-allyl- and 2-crotylindolines in high yields and diastereoselectivities.

    12. Switchable Materials

      Co–NC–W and Fe–NC–W Electron-Transfer Channels for Thermal Bistability in Trimetallic {Fe6Co3[W(CN)8]6} Cyanido-Bridged Cluster (pages 896–900)

      Dr. Robert Podgajny, Szymon Chorazy, Dr. Wojciech Nitek, Dr. Michał Rams, Anna M. Majcher, Bartosz Marszałek, Dr. Jan Żukrowski, Prof. Dr. Czesław Kapusta and Prof. Dr. Barbara Sieklucka

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201208023

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      Which way to choose? The trimetallic cyanide-bridged Fe6Co3W6 cluster serves as a molecular platform for two cooperating electron-transfer channels, WV–CN–HSCoII⇄WIV–CN–LSCoIII and WV–CN–HSFeII⇄WIV–CN–HSFeIII. {CoII3FeII6[WV(CN)8]6(MeOH)24}⋅x MeOH has a first-order unique spin transition with thermal charge-transfer-induced spin transition and spin bistability that is due to a specific distribution of Co and Fe sites.

    13. Bioinorganic Chemistry

      A Tetracarbene–Oxoiron(IV) Complex (pages 901–905)

      Steffen Meyer, Iris Klawitter, Dr. Serhiy Demeshko, Dr. Eckhard Bill and Prof. Dr. Franc Meyer

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201208044

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      Bioinspired organometallic chemistry: An oxoiron(IV) unit has been trapped within a macrocyclic tetracarbene ligand, merging a key bioinorganic intermediate with a popular organometallic scaffold (see picture). The stability of the new complex has allowed its characterization by a variety of methods, which show a strong σ-donating tetracarbene coordination leading to an S=1 ground state and unusual properties of the oxoiron(IV) species.

    14. Cycloaddition

      Regioselective Inter- and Intramolecular Formal [4+2] Cycloaddition of Cyclobutanones with Indoles and Total Synthesis of (±)-Aspidospermidine (pages 906–910)

      Mizuki Kawano, Takaaki Kiuchi, Shoko Negishi, Hiroyuki Tanaka, Takaya Hoshikawa, Prof. Dr. Jun-ichi Matsuo and Prof. Dr. Hiroyuki Ishibashi

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201206734

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      This way and that way: A formal [4+2] cycloaddition between various cyclobutanones and indoles proceeded efficiently under Lewis acid catalysis (see scheme; PG = protecting group). The regioselectivity of the reaction could be controlled in such a way that each of the two possible regioisomers of a cycloaddition product could be synthesized selectively. The usefulness of this reaction for the total synthesis of hydrocarbazole natural products was demonstrated.

    15. Synthetic Methods

      Rational Synthesis for All All-Homocalixarenes (pages 911–915)

      Dr. Alexander V. Predeus, Dr. Vijay Gopalsamuthiram, Dr. Richard J. Staples and Prof. William D. Wulff

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201206785

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      Have it all: The synthesis of homocalixarenes of all sizes has been demonstrated using the triple annulation of bis(carbene) complexes with diynes (see scheme). This strategy in principle should allow access to all homocalixarenes. The generality of the synthetic approach is also demonstrated by the preparation of a pyrrole-containing calixarene.

    16. Photocatalysis

      A Visible-Light-Harvesting Assembly with a Sulfocalixarene Linker between Dyes and a Pt-TiO2 Photocatalyst (pages 916–919)

      Dr. Takashi Kamegawa, Sachiyo Matsuura, Hiroki Seto and Prof. Dr. Hiromi Yamashita

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/anie.201206839

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      Successful anchoring of cationic dye molecules (thiazole orange, TO) on Pt-TiO2 for a visible-light-harvesting assembly was achieved by surface modification of Pt-TiO2 with 4-sulfocalix[4]arene as a linker, leading to formation of surface complexes (see picture). This heterogeneous system can act as an efficient photocatalyst for production of hydrogen in the presence of a sacrificial reagent (TEOA=triethanolamine).

    17. Biomimetic Model

      Aromatic Ring Cleavage of 2-Amino-4-tert-butylphenol by a Nonheme Iron(II) Complex: Functional Model of 2-Aminophenol Dioxygenases (pages 920–924)

      Biswarup Chakraborty and Dr. Tapan Kanti Paine

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/anie.201206922

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      Biomimetic aromatic ring cleavage: An iron(II)-2-aminophenolate complex (see picture, right) with a tetradentate ligand reacts with dioxygen to cleave the aromatic C[BOND]C bond of 2-amino-4-tert-butylphenolate to form 4-tert-butyl-2-picolinate. This complex represents a functional model of 2-aminophenol-1,6-dioxygenase (APD) and 3-hydroxyanthranilate-3,4-dioxygenase (HAD).

    18. Conduction in Bacterial Films

      Spectroscopic Slicing to Reveal Internal Redox Gradients in Electricity-Producing Biofilms (pages 925–928)

      Luciana Robuschi, Dr. J. Pablo Tomba, Germán D. Schrott, P. Sebastián Bonanni, P. Mariela Desimone and Dr. Juan Pablo Busalmen

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201205440

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      Wired-up bacteria: Confocal Raman microscopy in combination with 3D structural analysis is used in the measurement of redox gradients in electricity-producing biofilms in vivo. The approach provides new relevant information for the understanding of electron conduction mechanisms in these systems.

    19. Helical Structures

      Single Helicates of Dipalladium(II) Hexapyrroles: Helicity Induction and Redox Tuning of Chiroptical Properties (pages 929–932)

      Chaolu Eerdun, Satoshi Hisanaga and Prof. Jun-ichiro Setsune

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201207113

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      Hexapyrrole-α,ω-dialdehyde, which has eight donor atoms, afforded a dipalladium(II) single helicate (see picture; Pd pink, O red, N blue). A rapid interchange of the helical screw was slowed down by imine formation at the terminal aldehyde units with (R)-(−)-1-cyclohexylethylamine, leading to an overwhelming excess of a P-helical screw. This stable dinuclear single helicate has a redox-driven reversible change in chiroptical properties.

    20. Arene Alkylation

      Sterically Controlled Alkylation of Arenes through Iridium-Catalyzed C[BOND]H Borylation (pages 933–937)

      Daniel W. Robbins and Prof. John F. Hartwig

      Version of Record online: 11 DEC 2012 | DOI: 10.1002/anie.201208203

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      Complementary chemistry: A one-pot method for the site-selective alkylation of arenes controlled by steric effects is reported. The process occurs through Ir-catalyzed C[BOND]H borylation, followed by Pd- or Ni-catalyzed coupling with alkyl electrophiles. This selectivity complements that of the typical Friedel–Crafts alkylation; meta-selective alkylation of a broad range of arenes with various electronic properties and functional groups occurs in good yield with high site selectivity.

    21. Synthetic Methods

      Straightforward Synthetic Access to gem-Diaurated and Digold σ,π-Acetylide Species (pages 938–942)

      Adrián Gómez-Suárez, Stéphanie Dupuy, Prof. Dr. Alexandra M. Z. Slawin and Prof. Dr. Steven P. Nolan

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/anie.201208234

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      The more the merrier: Following previous investigations on the synthesis of organogold complexes by using [Au(IPr)(OH)], a high-yielding straightforward methodology for the synthesis of gem-diaurated and σ,π-acetylide species via a dinuclear gold hydroxide complex [{Au(IPr)}2(μ-OH)][BF4] (see scheme) has now been developed.

    22. Asymmetric Catalysis

      Chiral Phosphine Catalyzed Asymmetric Michael Addition of Oxindoles (pages 943–947)

      Fangrui Zhong, Xiaowei Dou, Xiaoyu Han, Weijun Yao, Qiang Zhu, Prof. Dr. Yuezhong Meng and Prof. Dr. Yixin Lu

      Version of Record online: 7 DEC 2012 | DOI: 10.1002/anie.201208285

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      Bifunctional phosphines derived from amino acids mediate the asymmetric Michael addition of 3-substituted oxindoles to activated alkenes (see scheme). Biologically relevant chiral 3,3-disubstituted oxindoles were thus prepared in high yields and with excellent enantioselectivities from 3-aryl- and 3-alkyl-substituted oxindoles and various activated alkenes.

    23. Asymmetric Synthesis

      A Concise Assembly of Electron-Deficient 2,4-Dienes and 2,4-Dienals: Regio- and Stereoselective exo-Diels–Alder and Redox Reactions through Sequential Amine and Carbene Catalysis (pages 948–951)

      Chao Ma, Zhi-Jun Jia, Jing-Xin Liu, Qing-Qing Zhou, Dr. Lin Dong and Prof. Dr. Ying-Chun Chen

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/anie.201208349

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      Ideal relay catalysis: A γ,δ-regioselective anomalous exo-Diels–Alder reaction with electron-deficient β-substituted 2,4-dienes and 2,4-dienals has been developed by using trienamine activation. The resulting multifunctional cycloadducts contain perfectly positioned functional groups, thereby facilitating a 1,5-hydride transfer from the C–H group of an aldehyde to an activated alkene under sequential catalysis of a carbene (see scheme).

    24. Natural Products

      Asymmetric Total Synthesis of Leucosceptroid B (pages 952–955)

      Xuan Huang, Liqiang Song, Jiao Xu, Guili Zhu and Prof. Dr. Bo Liu

      Version of Record online: 11 DEC 2012 | DOI: 10.1002/anie.201208687

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      Less stable, but natural: The asymmetric total synthesis of leucosceptroid B (see scheme) has been accomplished in 19 steps. Thermodynamically, this natural product proved to be less stable than its C11 epimer, a synthetic intermediate. This synthesis features a high degree of flexibility, facilitating its application to the preparation of a broad range of other natural derivatives.

    25. Constitutional Dynamic Materials

      Thermoresponsive Dynamic Covalent Single-Chain Polymer Nanoparticles Reversibly Transform into a Hydrogel (pages 956–959)

      Daniel E. Whitaker, Clare S. Mahon and Dr. David A. Fulton

      Version of Record online: 6 DEC 2012 | DOI: 10.1002/anie.201207953

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      To gel and back: Polymer nanoparticles can be reversibly transformed into a chemically cross-linked hydrogel. This transformation is triggered by the application of heat, which causes the polymer chains to aggregate, and the dynamic nature of the covalent cross-linking serves to reorganize the polymer chains into a hydrogel network.

    26. Rotaxanes

      Heterolytic Activation of H2 Using a Mechanically Interlocked Molecule as a Frustrated Lewis Base (pages 960–963)

      Christopher B. Caputo, Dr. Kelong Zhu, V. Nicholas Vukotic, Prof. Stephen J. Loeb and Prof. Douglas W. Stephan

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201207783

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      Frustrating: A sterically unencumbered aniline base (see picture, left) can be transformed into a bulky Lewis base by converting it into a [2]rotaxane (right). This Lewis base donor, which is surrounded by a protective macrocyclic ring, exhibits the reactivity of a frustrated Lewis pair (e.g. activation of H2(g)) without the need for direct covalent modification to increase its bulk.

    27. Electrocatalysis

      Towards More Active and Stable Electrocatalysts for Formic Acid Electrooxidation: Antimony-Decorated Octahedral Platinum Nanoparticles (pages 964–967)

      Dr. Francisco J. Vidal-Iglesias, Dr. Ana López-Cudero, Dr. José Solla-Gullón and Prof. Juan M. Feliu

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/anie.201207517

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      Antimony has it covered: Sb-decorated octahedral Pt nanoparticles have been prepared, and their electrocatalytic properties evaluated for formic acid electrooxidation. When tested at 0.2 V, these nanoparticles displayed high and stable current densities, as well as 35, five, and eight-fold current oxidation increases over bare octahedral and Sb-decorated spherical and cubic nanoparticles, respectively.

    28. Nanoparticles

      Ligand-Shell-Directed Assembly and Depolymerization of Patchy Nanoparticles (pages 968–972)

      Offer Zeiri, Dr. Yifeng Wang, Alevtina Neyman, Prof. Francesco Stellacci and Prof. Ira A. Weinstock

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/anie.201207177

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      Unprecedented insertions of cationic alkanethiols, HS(CH2)11N(CH3)3+ (see scheme; cyan-colored rods), between polyoxometalate protecting ligands, α-AlW11O399− (blue circles), and the surfaces of gold nanoparticles, give “zwitterionic” patchy nanoparticles (PNs). Their shell structures and assembly properties vary with particle size during rational in situ modifications that lead to three-component core–shell aggregates never observed before in PNs.

    29. Dye-Sensitized Solar Cells

      Using Orbital Symmetry to Minimize Charge Recombination in Dye-Sensitized Solar Cells (pages 973–975)

      Emanuele Maggio, Dr. Natalia Martsinovich and Prof. Alessandro Troisi

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201205184

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      Suitably designed symmetric dyes can be used in dye-sensitized solar cells to reduce the charge recombination rate by two to three orders of magnitude. If the electron coupling between the electrode and the dye is mediated by a conjugated linker, it is possible to design dyes for which the HOMO of the dye is not coupled to the semiconductor.

    30. Biosensors

      Enzyme-Encapsulating Quantum Dot Hydrogels and Xerogels as Biosensors: Multifunctional Platforms for Both Biocatalysis and Fluorescent Probing (pages 976–979)

      Dr. Jipei Yuan, Dr. Dan Wen, Dr. Nikolai Gaponik and Prof. Alexander Eychmüller

      Version of Record online: 22 NOV 2012 | DOI: 10.1002/anie.201205791

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      Trapped: Enzymes (blue in picture) were encapsulated into CdTe quantum dot (QD) hydrogels during the self-assembly of CdTe QDs (orange) in phosphate buffer solution. The as-prepared enzyme-encapsulating QD hydrogel incorporating both a biocatalysis unit and a fluorescence signaling unit was further explored as a multifunctional platform in the development of optical biosensors.

    31. Nanocrystals

      Selective Placement of Faceted Metal Tips on Semiconductor Nanorods (pages 980–982)

      Hendrik Schlicke, Dr. Debraj Ghosh, Lam-Kiu Fong, Dr. Huolin L. Xin, Dr. Haimei Zheng and Prof. A. Paul Alivisatos

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201205958

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      Squaring the circle: Carbon monoxide was used to grow faceted cube-like platinum tips on semiconductor nanorods (see scheme). These novel hybrid structures reveal a new degree of synthetic control and might allow control over the catalytic activity of nanoscale photocatalysts by adding defined faceting.

    32. Conjugation

      Cross-Hyperconjugation: An Unexplored Orbital Interaction between π-Conjugated and Saturated Molecular Segments (pages 983–987)

      Rikard Emanuelsson, Dr. Andreas Wallner, Eugene A. M. Ng, Prof. Joshua R. Smith, Dr. Djawed Nauroozi, Dr. Sascha Ott and Dr. Henrik Ottosson

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201206030

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      Crossing a barrier: Molecules with saturated ER2 units (E=C or Si, R=electron-releasing group) inserted between two π-conjugated segments have electronic and optical properties that resemble those of cross-conjugated molecules (see figure). This cross-hyperconjugation provides a deeper understanding of the conjugation phenomenon, and is an alternative to cross-conjugation in the design of molecules for nano and materials applications.

    33. Photocatalysis

      A Highly Efficient Mononuclear Iridium Complex Photocatalyst for CO2 Reduction under Visible Light (pages 988–992)

      Dr. Shunsuke Sato, Dr. Takeshi Morikawa, Dr. Tsutomu Kajino and Prof. Osamu Ishitani

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/anie.201206137

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      Mononuclear iridium(III) terpyridine (tpy) 2-phenylpyridine (ppy) complexes [Ir(tpy)(R-ppy)Cl] (R=H, Me, CF3) can act as efficient and selective CO2 reduction photocatalysts. The reaction is driven using visible light in a homogeneous solution, and even in a H2O mixed solution. The most efficient photocatalyst is [Ir(tpy)(Me-ppy)Cl], for which the turnover in CO was over 50 and the quantum yield was 0.21 at 480 nm.

    34. Density Functional Calculations

      Nitrogen Inversion Barriers Affect the N-Oxidation of Tertiary Alkylamines by Cytochromes P450 (pages 993–997)

      Dr. Patrik Rydberg, Martin S. Jørgensen, Dr. Thomas A. Jacobsen, Dr. Anne-Marie Jacobsen, Dr. Kim G. Madsen and Dr. Lars Olsen

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201206207

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      Calculations: Cytochrome P450 enzymes facilitate a number of chemically different reactions. For example, amines can be either N-dealkylated or N-oxidized, but it is complex to rationalize which of these competing reactions occurs. It is shown that the barrier for inversion of the alkylamine nitrogen atom seems to be of vital importance for the amount of N-oxidized product formed relative to dealkylation and hydroxylation products.

    35. Dynamic Frameworks

      Dynamic Structural Behavior and Anion-Responsive Tunable Luminescence of a Flexible Cationic Metal–Organic Framework (pages 998–1002)

      Biplab Manna, Abhijeet K. Chaudhari, Biplab Joarder, Avishek Karmakar and Dr. Sujit K. Ghosh

      Version of Record online: 5 DEC 2012 | DOI: 10.1002/anie.201206724

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      Guest and anion dependent: Structural dynamism and luminescence of a cationic porous framework (see picture) are investigated by different analytical techniques, such as single-crystal-to-single-crystal structural transformation. The compound shows size-selective sorption of hydrophobic guest molecules, easy exchange of anions of the framework, and interesting anion-responsive luminescence.

    36. Ruthenium Catalysis

      One-Pot Ring-Closing Metathesis/1,3-Dipolar Cycloaddition through Assisted Tandem Ruthenium Catalysis: Synthesis of a Dye with Isoindolo[2,1-a]quinoline Structure (pages 1003–1007)

      Dr. Mitsuhiro Arisawa, Yuki Fujii, Hiroshige Kato, Dr. Hayato Fukuda, Dr. Takashi Matsumoto, Mika Ito, Dr. Hiroshi Abe, Dr. Yoshihiro Ito and Prof. Dr. Satoshi Shuto

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/anie.201206765

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      The one-pot tandem reaction of N-alkyl-N-allyl-2-vinylaniline derivatives with benzo- or naphthoquinones and a ruthenium–alkylidene catalyst leads to isoindolo[2,1-a]quinolines in a variety of colors, which can be altered by exchanging the substituent on the core heterocycle (see scheme). This reaction offers a new synthetic method for π-conjugated small molecules from simple aniline derivatives.

    37. Controlled Cargo Release

      You have full text access to this OnlineOpen article
      Light-Triggered Sequence-Specific Cargo Release from DNA Block Copolymer–Lipid Vesicles (pages 1008–1012)

      Dr. Alberto Rodríguez-Pulido, Alina I. Kondrachuk, Dr. Deepak K. Prusty, Jia Gao, Prof. Dr. Maria A. Loi and Prof. Dr. Andreas Herrmann

      Version of Record online: 26 OCT 2012 | DOI: 10.1002/anie.201206783

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      Vesicle buster: Versatile functionalized nanocontainers, based on the stable incorporation of 22 mer DNA-b-PPO block copolymers (DBCs) into lipid vesicles, are presented (see picture). The study shows effective and sequence-specific cargo release from the DBC–lipid vesicles. Hybridization of these vesicles with an oligonucleotide photosensitizer allows for singlet oxygen generation upon irradiation, which induces cargo release.

    38. Stereodynamics

      Orientation Effect in the Low-Energy Electron Attachment to the Apolar Carbon Tetrafluoride Molecule (pages 1013–1016)

      Lei Xia, Xian-Jin Zeng, Hong-Kai Li, Bin Wu and Prof. Dr. Shan Xi Tian

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201206948

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      Electron capture at the carbon–fluorine σ* antibonding orbital accounts for the vector correlations between fragments F and CF3 or F and CF3 in two complementary dissociation pathways after electron attachment to CF4. An orientation effect in the low-energy electron attachment is observed by velocity mapping (see picture; C black, F blue).

    39. Systems Chemistry

      Transformations within a Network of Cadmium Architectures (pages 1017–1021)

      Wenjing Meng, Dr. Tanya K. Ronson, Dr. Jack K. Clegg and Dr. Jonathan R. Nitschke

      Version of Record online: 13 DEC 2012 | DOI: 10.1002/anie.201206990

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      CdII transformer: By using a linear dialdehyde, CdII ions, and different amines, different architectures were constructed, including an M2L34+ triple helicate, an M3L36+ triangle, an M4L8+ cryptate, as well as an M12L1824+ hexagonal prism. These structures could be interconverted in a complex network by dynamic imine exchange, the addition of a template, or a change in the pH value of the solution.

    40. Protein Perdeuteration

      Near-Atomic Resolution Neutron Crystallography on Perdeuterated Pyrococcus furiosus Rubredoxin: Implication of Hydronium Ions and Protonation State Equilibria in Redox Changes (pages 1022–1025)

      Dr. M. G. Cuypers, Dr. S. A. Mason, Dr. M. P. Blakeley, Prof. E. P. Mitchell, Dr. M. Haertlein and Prof. V. Trevor Forsyth

      Version of Record online: 6 DEC 2012 | DOI: 10.1002/anie.201207071

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      Neutron crystallographic analyses at near-atomic resolution are presented for both reduced and oxidized forms of perdeuterated Pyrococcus furiosus rubredoxin, a small iron–sulfur redox protein with remarkable thermostability. Hydronium ions may play a key role in the protonation and charge-transfer processes associated with the oxidized and reduced forms of the protein. Picture: overall structure showing D3O+ ions (red and gray molecules).

    41. Oxygen-Reduction Catalysts

      A Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction: N-Doped Ketjenblack Incorporated into Fe/Fe3C-Functionalized Melamine Foam (pages 1026–1030)

      Jang-Soo Lee, Gi Su Park, Sun Tai Kim, Prof. Dr. Meilin Liu and Prof. Dr. Jaephil Cho

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201207193

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      Inspired by the tetrapod structures of a breakwater, a highly efficient electrocatalyst for oxygen reduction reaction (ORR) in alkaline solution has been created from low-cost, commercial melamine foam and ketjenblack. The unique porous architecture greatly facilitates rapid mass transport, while the N-doped ketjenblack and Fe/Fe3C-functionalized surface of the framework dramatically enhance the ORR activity.

    42. Liquid Crystals

      Amphiphilic Design of a Discotic Liquid-Crystalline Molecule for Dipole Manipulation: Hierarchical Columnar Assemblies with a 2D Superlattice Structure (pages 1031–1034)

      Ming-Che Yeh, Yu-Lou Su, Mei-Chun Tzeng, Prof. Dr. Chi Wi Ong, Dr. Takashi Kajitani, Dr. Hideo Enozawa, Prof. Dr. Masaki Takata, Dr. Yoshiko Koizumi, Dr. Akinori Saeki, Prof. Dr. Shu Seki and Prof. Dr. Takanori Fukushima

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201207708

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      A liquid-crystalline dibenzophenazine that was forced to adopt a head-to-head stacking arrangement to generate a large dipole moment adapted to this stacking by hierarchical assembly into a 2D hexagonal superlattice (see picture). Thus, the net dipole and the contact area between immiscible side chains were minimized. Homeotropic alignment of the assembly on glass gave rise to directional charge transport.

    43. Photocatalysis

      Chlorine-Radical-Mediated Photocatalytic Activation of C[BOND]H Bonds with Visible Light (pages 1035–1039)

      Dr. Rusheng Yuan, Shaolong Fan, Huaxi Zhou, Dr. Zhengxin Ding, Dr. Sen Lin, Prof. Dr. Zhaohui Li, Dr. Zizhong Zhang, Dr. Chao Xu, Prof. Ling Wu, Prof. Xuxu Wang and Prof. Xianzhi Fu

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201207904

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      Going green on the cheap: A highly effective photocatalytic reaction mode involving chlorine radicals generated on chlorinated BiOBr/TiO2 upon irradiation with visible light enabled selective transformations of alkanes into functionalized products through the formation of C[BOND]O and C[BOND]C bonds (see scheme). This process provides a sustainable strategy for direct C[BOND]H functionalization under mild conditions.

    44. Metal-Free Alkane Transformation

      Carbon–Carbon Bond Activation in Saturated Hydrocarbons by Field-Assisted Nitrogen Fixation (pages 1040–1043)

      Guangtao Li, Dr. Xin Li, Prof. Zheng Ouyang and Prof. R. Graham Cooks

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201207997

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      Functionalization of alkanes: Waxes present on electrically charged surfaces undergo C[BOND]C bond functionalization with N2 to give imines. The products are characterized on-line by mass spectrometry or collected and characterized off-line by Raman spectroscopy (see picture).

    45. Aromaticity

      Ruthenocenoporphyrinoids: Conformation Determines Macrocyclic π Conjugation Transmitted Across a d-Electron Metallocene (pages 1044–1048)

      Irena Grocka, Prof. Lechosław Latos-Grażyński and Dr. Marcin Stępień

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201208289

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      Hinges upon Ru: The hingelike flexibility of ruthenocene plays the critical role as a determinant of aromaticity as exemplified by its aromatic synperiplanar and antiaromatic anticlinal(eclipsed) conformers of ruthenocenoporphyrinoids (see figure).

    46. Molecular Wires

      Electrical Switching Behavior of a [60]Fullerene-Based Molecular Wire Encapsulated in a Syndiotactic Poly(methyl methacrylate) Helical Cavity (pages 1049–1053)

      Dr. Shengli Qi, Dr. Hiroki Iida, Dr. Lili Liu, Prof. Stephan Irle, Prof. Wenping Hu and Prof. Eiji Yashima

      Version of Record online: 13 DEC 2012 | DOI: 10.1002/anie.201208481

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      Exploding peapods? A helical syndiotactic poly(methyl methacrylate) encapsulates C60 molecules within its helical cavity to form a supramolecular peapod-like molecular wire. Sandwich devices using these molecular wires in the active layer exhibit an irreversible electrical switching effect. Calculations predict a violent Coulomb explosion in the peapod C60 wires during the charge injection process, which would account for the observed irreversible electrical switching.

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