Chemistry – An Asian Journal

Cover image for Vol. 9 Issue 4

April 2014

Volume 9, Issue 4

Pages 929–1189

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Focus Reviews
    7. Communications
    8. Full Papers
    1. You have free access to this content
      Cover Picture: Extended Conjugated Donor–Acceptor Molecules with E-(1,2-Difluorovinyl) and Diketopyrrolopyrrole (DPP) Moieties toward High-Performance Ambipolar Organic Semiconductors (Chem. Asian J. 4/2014) (page 929)

      Zhengxu Cai, Hewei Luo, Xin Chen, Dr. Guanxin Zhang, Dr. Zitong Liu and Prof. Dr. Deqing Zhang

      Version of Record online: 21 MAR 2014 | DOI: 10.1002/asia.201490008

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      Ambipolar organic semiconductors that can conduct both hole and electron carriers have received increasing attention in recent years. In their Full Paper on page 1068 ff., Deqing Zhang and co-workers report two conjugated molecules containing E-(1,2-difluorovinyl) and diketopyrrolopyrrole (DPP) moieties. One of them, DPP-2F, displays an ambipolar semiconducting behavior with hole and electron mobilities reaching 0.42 and 0.80 cm2 V−1 s−1, respectively. The present study clearly demonstrates that (E)-2-(1,2-difluorovinyl) is a useful electron-withdrawing block to tune frontier orbital energies and extend conjugation.

    2. You have free access to this content
      Inside Cover: Thieno[3,4-c]pyrrole-4,6-dione-Based Small Molecules for Highly Efficient Solution-Processed Organic Solar Cells (Chem. Asian J. 4/2014) (page 930)

      Jong-jin Ha, Yu Jin Kim, Jong-gwang Park, Tae Kyu An, Prof. Soon-Ki Kwon, Prof. Chan Eon Park and Prof. Yun-Hi Kim

      Version of Record online: 21 MAR 2014 | DOI: 10.1002/asia.201490009

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      Solar Cells Small-molecule organic solar cells (SMOSCs) have recently gained attention as sources of renewable energy owing to their advantages such as easier synthesis, less batch-to-batch variation, and better reproducibility with regard to performance as compared to polymer-based solar cells. In their Full Paper on page 1045 ff., highlighted on the Inside Cover, Yun-Hi Kim et al. designed and synthesized two small molecules bearing a thieno[3,4-c]pyrrole-4,6-dione (TPD) unit. These compounds show an excellent thermal stability, strong absorption, relatively low HOMO levels, and high hole mobility. SMOSCs based on blends of these donor molecules and a phenyl-C61-butyric acid methyl ester acceptor display power conversion efficiencies as high as 4.6 %.

  2. Graphical Abstract

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Focus Reviews
    7. Communications
    8. Full Papers
    1. You have free access to this content
      Corrigendum: Iron- and Bismuth-Catalyzed Asymmetric Mukaiyama Aldol Reactions in Aqueous Media (pages 942–943)

      Taku Kitanosono, Prof. Dr. Thierry Ollevier and Prof. Dr. Shū Kobayashi

      Version of Record online: 21 MAR 2014 | DOI: 10.1002/asia.201400098

      This article corrects:

      Iron- and Bismuth-Catalyzed Asymmetric Mukaiyama Aldol Reactions in Aqueous Media

      Vol. 8, Issue 12, 3051–3062, Version of Record online: 2 OCT 2013

  4. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Focus Reviews
    7. Communications
    8. Full Papers
    1. Hypervalent Iodine Catalysis

      Hypervalent Iodine-Catalyzed Oxidative Functionalizations Including Stereoselective Reactions (pages 950–971)

      Dr. Fateh V. Singh and Prof. Dr. Thomas Wirth

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/asia.201301582

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      Hypervalent iodine reagents have a wide range of reactivities and can be used under mild reaction conditions. Their applications in catalysis have led to a number of oxidative transformations that are summarized here. Hypervalent iodine catalysts generated in situ by oxidation of iodoarenes with stoichiometric oxidants such as m-chloroperbenzoic acid or oxone allow metal-free and environmentally friendly reactions.

    2. Hypervalent Iodine Reagents

      Vicinal Difunctionalization of Alkenes with Iodine(III) Reagents and Catalysts (pages 972–983)

      R. Martín Romero, Dr. Thorsten H. Wöste and Prof. Dr. Kilian Muñiz

      Version of Record online: 3 MAR 2014 | DOI: 10.1002/asia.201301637

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      I am hyper all the time: Homogeneous oxidation reactions that convert simple alkenes into 1,2-difunctionalized products can be realized with a series of hypervalent iodine(III) reagents. This review provides an overview over recent developments in the field, covering both new methodology as well as the development of enantioselective transformations.

    3. Cooperative Catalysis

      Synergy, Compatibility, and Innovation: Merging Lewis Acids with Stereoselective Enamine Catalysis (pages 984–995)

      Dr. Andrea Gualandi, Luca Mengozzi, Claire M. Wilson and Prof. Pier Giorgio Cozzi

      Version of Record online: 23 FEB 2014 | DOI: 10.1002/asia.201301549

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      The Perfect Storm! Water facilitates catalyst turnover in enamine organocatalysis, and it is generated during enamine formation. A synergy between Lewis acids and organocatalysts allows for the development of new, selective, and innovative processes, but water-compatible Lewis acids must be employed that are capable of surviving and maintaining activity in the presence of water.

  6. Communications

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

      Switchable Dielectric Phase Transition Induced by a Twisting Transformation in Diglycine Methanesulfonate (pages 996–1000)

      Pan Zhou, Dr. Zhihua Sun, Dr. Shuquan Zhang, Tianliang Chen, Chengmin Ji, Dr. Sangen Zhao and Prof. Junhua Luo

      Version of Record online: 2 FEB 2014 | DOI: 10.1002/asia.201301655

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      The new glycine-based compound diglycine methanesulfonate undergoes a reversible second-order phase transition at 134 K (Tc), triggered by the twisting transformation of the molecules, and exhibits a distinct contrast between the high and low-dielectric state with exceptional anisotropies along different crystal axes.

    2. Molecular Recognition

      Enhancement of Host–Guest Interactions Using Rationally Designed Macrocyclic Boronic Esters with a Naphthalene Core (pages 1001–1005)

      Yuji Kikuchi, Dr. Hiroki Takahagi, Dr. Kosuke Ono and Prof. Dr. Nobuharu Iwasawa

      Version of Record online: 2 FEB 2014 | DOI: 10.1002/asia.201301577

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      What makes a good host? Efficient inclusion of electron-deficient aromatic molecules in organic solvent utilizing π-stacking interactions was achieved by using 1,4-naph-[2+2] or 1,5-naph-[2+2]. Owing to the parallel two naphthalene rings, 1,5-naph-[2+2] has a much higher binding ability than 1,4-naph-[2+2].

    3. Nanoparticles

      Chemico-Physical Synthesis of Surfactant- and Ligand-Free Gold Nanoparticles and Their Anti-Galvanic Reduction Property (pages 1006–1010)

      Man Wang, Prof. Dr. Zhikun Wu, Prof. Zhaoqin Chu, Jie Yang and Chuanhao Yao

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/asia.201301562

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      Anti-galvanic reduction: Surfactant- and ligand-free gold nanoparticles (AuNPs) were obtained by a combination of chemical and physical methods. It was found that the as-prepared AuNPs can reduce silver ions and copper ions, which illustrates that anti-galvanic reduction (AGR) is not dependent on reductive ligands. Importantly, the Raman scattering signals of Rhodamine 6G were distinctly enhanced on the AuNPs after AGR.

    4. Yolk–Shell Structures

      Excellent Electrochemical Properties of Yolk–Shell MoO3 Microspheres Formed by Combustion of Molybdenum Oxide–Carbon Composite Microspheres (pages 1011–1015)

      You Na Ko, Prof. Dr. Seung Bin Park and Prof. Yun Chan Kang

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/asia.201301541

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      Great eggs from fire: Yolk–shell structured MoO3 microspheres are prepared in a facile two-step process and used as anode material for Li-ion batteries. In the two-step preparation, molybdenum oxide–carbon (MoOx–C) composite microspheres are first obtained by spray pyrolysis. Combustion at 400 °C in air yields the core@void@shell structures.

    5. Macrocycles

      A Solvato-Fluorochromic Macrocycle of Multiple Anthracene Fluorophores in Close Proximity (pages 1016–1019)

      Dr. Zhiou Li, Dr. Yoshihisa Sei, Prof. Munetaka Akita and Dr. Michito Yoshizawa

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/asia.201301648

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      Let′s twist again: A fluorescent macrocycle containing four anthracene panels linked by meta-phenylene spacers and amino hinges was synthesized. The macrocycle adopts a twisted, compressed conformation that places embedded anthracene fluorophores in close contact. Emission from the convoluted macrocycle is highly solvatochromic and significantly enhanced as compared with that of the partial structures.

    6. Phosphorescence

      Cr3+:SrGa12O19: A Broadband Near-Infrared Long-Persistent Phosphor (pages 1020–1025)

      Ju Xu, Prof. Daqin Chen, Dr. Yunlong Yu, Wenjuan Zhu, Jiangchong Zhou and Prof. Yuansheng Wang

      Version of Record online: 24 FEB 2014 | DOI: 10.1002/asia.201400009

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      Shine on! A near-infrared broadband long-persistent Cr3+:SrGa12O19 phosphor is successfully fabricated for the first time. After UV irradiation (250–400 nm), the phosphorescence can last for 2 h. This effect is ascribed to the persistent energy transfer from the SrGa12O19 host to the Cr3+ ions, and the filling and release of electrons into and from the shallow and deep traps, assisted by the conduction band.

    7. Fluorescence

      Synthesis of Pyridine N-Oxide–BF2CF3 Complexes and Their Fluorescence Properties (pages 1026–1030)

      Tomoaki Nishida, Dr. Aiko Fukazawa, Eriko Yamaguchi, Hiroya Oshima, Prof. Dr. Shigehiro Yamaguchi, Prof. Dr. Motomu Kanai and Prof. Dr. Yoichiro Kuninobu

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/asia.201301688

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      Too complex for simple answers: Complexes of pyridine N-oxide with BF2CF3 and BF2C2F5, and their derivatives were synthesized. Most of the complexes fluoresce, both in solution and in the solid state. By expanding the π-conjugated skeleton, the color of the fluorescence could be changed dramatically. Owing to their properties such complexes hold potential as organic functional materials.

  7. Full Papers

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

      Interactions between Freons: A Rotational Study of CH2F2–CH2Cl2 (pages 1032–1038)

      Qian Gou, Lorenzo Spada, Montserrat Vallejo-López, Prof. Zbigniew Kisiel and Prof. Walther Caminati

      Version of Record online: 26 FEB 2014 | DOI: 10.1002/asia.201301722

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      Turner prize: The rotational spectrum of the difluoromethane–dichloromethane adduct displays a hyperfine structure, which indicates that the two chlorine atoms are equivalent. The two subunits are linked together through a network of one C[BOND]H⋅⋅⋅F[BOND]C and two C[BOND]H⋅⋅⋅Cl[BOND]C weak hydrogen bonds.

    2. Macrocyclization

      Tetrathiafulvalene-Based Macrocycles Formed by Radical Cation Dimerization: The Role of Intramolecular Hydrogen Bonding and Solvent (pages 1039–1044)

      Wei-Kun Wang, Yuan-Yuan Chen, Dr. Hui Wang, Prof. Dr. Dan-Wei Zhang, Prof. Dr. Yi Liu and Prof. Dr. Zhan-Ting Li

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/asia.201301729

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      A dime(rization) a dozen: Inherently weak dimerization of tetrathiafulvalene (TTF) radical cations can be strengthened remarkably if two TTF units are attached to a hydrogen-bonding-driven aromatic amide foldamer segment and oxidized to TTF⋅+. The dimerization can lead to the formation of a uni- or bimolecular noncovalent macrocycle, depending on the polarity of the solvent.

    3. Solar Cells

      Thieno[3,4-c]pyrrole-4,6-dione-Based Small Molecules for Highly Efficient Solution-Processed Organic Solar Cells (pages 1045–1053)

      Jong-jin Ha, Yu Jin Kim, Jong-gwang Park, Tae Kyu An, Prof. Soon-Ki Kwon, Prof. Chan Eon Park and Prof. Yun-Hi Kim

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/asia.201301357

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      Powering up: Two small molecules named BT-TPD and TBDT-TTPD with a thieno[3,4-c]pyrrole-4,6-dione (TPD) unit are designed and synthesized for solution-processed bulk-heterojunction solar cells. Small-molecule organic solar cells based on blends of these donor molecules and a phenyl-C61-butyric acid methyl ester acceptor display power conversion efficiencies (η) as high as 4.62 %.

    4. Nanostructures

      Synthesis of Ultra-Stable Fluorescent Carbon Dots from Polyvinylpyrrolidone and Their Application in the Detection of Hydroxyl Radicals (pages 1054–1059)

      Xiangling Ren, Jing Liu, Dr. Xianwei Meng, Jianfei Wei, Dr. Tianlong Liu and Prof. Fangqiong Tang

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/asia.201301419

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      Dot to dot: Highly biocompatible and highly photostable fluorescent carbon dots (quantum yield up to 23.58 %) were obtained through a simple and nontoxic one-pot hydrothermal method. The resulting carbon dots have been demonstrated as an excellent probe for the sensing of hydroxyl radicals (see figure).

    5. Ring Expansion

      Nucleophile-Dependent Regio- and Stereoselective Ring Opening of 1-Azoniabicyclo[3.1.0]hexane Tosylate (pages 1060–1067)

      Mi-Kyung Ji, Dietmar Hertsen, Doo-Ha Yoon, Heesung Eum, Hannelore Goossens, Prof. Dr. Michel Waroquier, Prof. Dr. Veronique Van Speybroeck, Prof. Dr. Matthias D'hooghe, Prof. Dr. Norbert De Kimpe and Prof. Dr. Hyun-Joon Ha

      Version of Record online: 2 FEB 2014 | DOI: 10.1002/asia.201301551

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      A ring thing: 1-[(1R)-(1-Phenylethyl)]-1-azoniabicyclo[3.1.0]hexane tosylate generated from 2-(3-hydroxypropyl)aziridine with p-toluenesulfonyl anhydride was treated with various nucleophiles including halide, azide, acetate, and cyanide in CH3CN to afford either piperidines or pyrrolidines through regio- and stereoselective ring opening (see scheme).

    6. Donor–Acceptor Systems

      Extended Conjugated Donor–Acceptor Molecules with E-(1,2-Difluorovinyl) and Diketopyrrolopyrrole (DPP) Moieties toward High-Performance Ambipolar Organic Semiconductors (pages 1068–1075)

      Zhengxu Cai, Hewei Luo, Xin Chen, Dr. Guanxin Zhang, Dr. Zitong Liu and Prof. Dr. Deqing Zhang

      Version of Record online: 23 JAN 2014 | DOI: 10.1002/asia.201301312

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      Do behave! New π-extended diketopyrrolopyrrole (DPP)-based D–A conjugated molecules, DPP-F and DPP-2F (see picture), are reported. The LUMO energies and band gaps of DPP-F and DPP-2F are lowered by the introduction of E-(1,2-difluorovinyl) moieties. Thin-film organic field-effect transistors of DPP-2F display ambipolar semiconducting behavior, whereas DPP-F exhibits p-type semiconducting behavior.

    7. Encapsulation

      Hydrogen-Bond and Metal–Ligand Coordination Bond Hybrid Supramolecular Capsules: Identification of Hemicapsular Intermediate and Dual Control of Guest Exchange Dynamics (pages 1076–1082)

      Yuki Nito, Hirofumi Adachi, Naoaki Toyoda, Prof. Hikaru Takaya, Prof. Kenji Kobayashi and Prof. Masamichi Yamanaka

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/asia.201301628

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      Capsule corporation: Hybrid supramolecular capsules self-assemble by simultaneously forming hydrogen and metal–ligand coordination bonds on mixing a C2-symmetrical cavitand and a metal complex in 1:1 ratio (see figure). In the presence of excess amounts of cavitand, a hemicapsular assembly is identified as an intermediate. Variations in the structure of the metal complex and amount of polar solvent exert dual control on the dynamics of guest exchange.

    8. Cage Compounds

      Synthesis and Characterization of Two Discrete Ln10 Nanoscopic Ladder-Type Cages: Magnetic Studies Reveal a Significant Cryogenic Magnetocaloric Effect and Slow Magnetic Relaxation (pages 1083–1090)

      Amit Adhikary, Dr. Himanshu Sekhar Jena, Sajal Khatua and Dr. Sanjit Konar

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/asia.201301619

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      Top of the ladder: Two lanthanide-based nanoscopic cages [Ln10] have been synthesized. Structural characterization of [Gd10] reveals an aesthetically pleasing ladder-type cage (see figure). Magnetic investigation reveals that [Gd10] is a good candidate for magnetic refrigeration with a significant entropy change, whereas [Dy10] shows single-molecule magnet (SMM)-like behavior.

    9. Host–Guest Systems

      The Influence of the Framework: An Anion-Binding Study Using Fused [n]Polynorbornanes (pages 1091–1098)

      Benjamin M. Long and Dr. Frederick M. Pfeffer

      Version of Record online: 13 FEB 2014 | DOI: 10.1002/asia.201301677

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      One anion or two? A series of bis-thiourea-functionalized [n]polynorbornane hosts (16) with increasing size were synthesized and their anion-binding properties were evaluated by using 1H NMR spectroscopic titration and Job's plot analysis. Our results highlight the subtle influence that the framework itself can have on host–guest interactions.

    10. Block Copolymers

      Consequences of Block Sequence on the Orthogonal Folding of Triblock Copolymers (pages 1099–1107)

      Dr. Nobuhiko Hosono, Dr. Patrick J. M. Stals, Dr. Anja R. A. Palmans and Prof. Dr. E. W. Meijer

      Version of Record online: 23 FEB 2014 | DOI: 10.1002/asia.201400011

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      ABA- and BAB-type triblock copolymers carrying distinct self-assembling motifs in each block were designed and synthesized. These polymers fold into single-chain polymeric nanoparticles via thermal and photoirradiation treatments. An influence of block sequence on the folded structure is found, which affects the packing size of the resulting folded nanoparticles (see figure).

    11. Diastereoselectivity

      Silicon-Based Bulky Group-Induced Remote Control and Conformational Preference in the Synthesis and Application of Isolable Atropisomeric Amides with Secondary Alcohol or Amine Moieties (pages 1108–1115)

      Xing-Feng Bai, Wen-Hui Deng, Dr. Zheng Xu, Prof. Dr. Fu-Wei Li, Dr. Yuan Deng, Prof. Dr. Chun-Gu Xia and Prof. Dr. Li-Wen Xu

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/asia.201301727

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      You own the remote control: The interactional reactivity between a silicon-based bulky group and an O-/N-containing functional group has been determined by lateral lithiation–substitution, desilylation, and desilylation–olefination with benzaldehyde, thus revealing the considerable role of information transmission and steric hindrance in the controllable and diastereoselective synthesis of atropisomeric molecules.

    12. Magnetic Properties

      Low-Dimensional Carboxylate-Bridged GdIII Complexes for Magnetic Refrigeration (pages 1116–1122)

      Dr. Sui-Jun Liu, Chen-Chao Xie, Ji-Min Jia, Jiong-Peng Zhao, Song-De Han, Yu Cui, Yue Li and Prof. Dr. Xian-He Bu

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/asia.201301586

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      Building bridges: Four carboxylate-based GdIII complexes without long-range magnetic ordering show large magnetocaloric effects, owing to relatively low Mw/NGd ratios and weak exchange interactions. All of them (especially the citric acid derivative) have great potential application in molecular magnetic refrigeration.

    13. Chalcogenides

      Synthesis, Structure and Bonding, Optical Properties of Ba4MTrQ6 (M=Cu, Ag; Tr=Ga, In; Q=S, Se) (pages 1123–1131)

      Xiao-Wu Lei, Min Yang, Prof. Dr. Sheng-Qing Xia, Xiao-Cun Liu, Ming-Yan Pan, Xin Li and Xu-Tang Tao

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/asia.201301495

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      Some of these things are not like the others: Despite similar chemical compositions, the quaternary chalcogenides Ba4AgGaQ6 (Q=S, Se) and Ba4MInS6 (M=Cu, Ag) exhibit three different but closely related structures because of the arrangement of the transition metals and the triel atoms in the polyanionic chains and because of their stacking modes. Electronic band structure calculations help to understand the structures of these phases.

    14. Oxidation

      Cobalt Complexes with Pyrazole Ligands as Catalyst Precursors for the Peroxidative Oxidation of Cyclohexane: X-ray Absorption Spectroscopy Studies and Biological Applications (pages 1132–1143)

      Dr. Telma F. S. Silva, Prof. Luísa M. D. R. S. Martins, Prof.  M. Fátima C. Guedes da Silva, Dr. Maxim L. Kuznetsov, Prof. Alexandra R. Fernandes, Ana Silva, Dr. Chun-Jern Pan, Dr. Jyh-Fu Lee, Prof. Bing-Joe Hwang and Prof. Armando J. L. Pombeiro

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/asia.201301331

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      Oxidizing cyclohexane: CoII–pyrazole complexes are catalyst precursors for the partial oxidation of cyclohexane with H2O2. The catalytic activity tends to increase with a decrease in the oxidation potential and the absence of basic substituents. In situ X-ray absorption spectroscopy studies suggest the involvement of a common oxidized mononuclear CoIII species. The complexes show in vitro cytotoxicity toward some human cancer cell lines.

    15. Carbon Nanotubes

      Critical Evaluation of Adsorption–Desorption Hysteresis of Heavy Metal Ions from Carbon Nanotubes: Influence of Wall Number and Surface Functionalization (pages 1144–1151)

      Dr. Jie Li, Dr. Changlun Chen, Dr. Shouwei Zhang, Dr. Xuemei Ren, Dr. Xiaoli Tan and Prof. Xiangke Wang

      Version of Record online: 2 FEB 2014 | DOI: 10.1002/asia.201301475

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      Why would heavy metal ever go away? The adsorption of heavy metal ions on single-, double-, and multi-walled carbon nanotubes (SWCNTs, DWCNTs, and MWCNTs), and two oxidized MWCNTs with different oxygen contents as well as the corresponding desorption hysteresis were investigated. It was found that the adsorption–desorption hysteresis is dependent on the wall number and surface functionalization of CNTs, solution pH, and temperature.

    16. Bridging Ligands

      Bridge-Localized HOMO-Binding Character of Divinylanthracene-Bridged Dinuclear Ruthenium Carbonyl Complexes: Spectroscopic, Spectroelectrochemical, and Computational Studies (pages 1152–1160)

      Ya-Ping Ou, Jing Zhang, Meng Xu, Jianlong Xia, Prof. František Hartl, Prof. Dr. Jun Yin, Prof. Dr. Guang-Ao Yu and Prof. Dr. Sheng Hua Liu

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/asia.201301544

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      Spanning the gap: The electronic properties of four divinylanthracene-bridged diruthenium carbonyl complexes were investigated by IR and UV/Vis/near-IR spectroelectrochemistry (see picture). The results strongly support the redox noninnocent character of the bridging ligand. EPR spectroscopy of four singly oxidized complexes generated by a chemical oxidation method at room temperature reveals a largely ligand-centered spin.

    17. Layered Compounds

      Preparation of Monodisperse Ferrite Nanocrystals with Tunable Morphology and Magnetic Properties (pages 1161–1167)

      Ruizheng Liang, Rui Tian, Zhihui Liu, Dr. Dongpeng Yan and Prof. Min Wei

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/asia.201301590

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      Crystal clear: Dibasic spinel MFe2O4 (M=Mg, Ni, Co, Fe, Mn) and polybasic spinel MCoFeO4 (M=Mg, Ni, Mn, MgNi) nanocrystals with finely tuned composition, morphology, and particle size were prepared by the calcination of layered double hydroxide precursors at 900 °C (see figure), which could be potentially used in magnetic and biological fields.

    18. Ligands

      Synthesis of New Diphosphine Ligands and their Application in Pd-Catalyzed Alkoxycarbonylation Reactions (pages 1168–1174)

      Dr. Anahit Pews-Davtyan, Xianjie Fang, Dr. Ralf Jackstell, Dr. Anke Spannenberg, Dr. Wolfgang Baumann, Prof. Dr. Robert Franke and Prof. Dr. Matthias Beller

      Version of Record online: 2 FEB 2014 | DOI: 10.1002/asia.201301636

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      So much potential: Carbocyclic and N-heterocyclic analogues of bis(di-tert-butylphosphinomethyl) benzene (1) have been synthesized in moderate to very good yields. The new ligands demonstrated their catalytic potential in palladium-catalyzed methoxycarbonylation of 1-octene.

    19. Cytochromes

      Metabolism of Halogenated Alkanes by Cytochrome P450 enzymes. Aerobic Oxidation versus Anaerobic Reduction (pages 1175–1182)

      Dr. Li Ji, Jing Zhang, Prof. Dr. Weiping Liu and Dr. Sam P. de Visser

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/asia.201301608

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      Transcending barriers: We investigated the oxidative and reductive P450 activation of CCl4 and CHCl3 as halogenated models with DFT methods. An oxidative halosylation mechanism was proposed for CCl4 by Cpd I of P450, while the metabolism of CHCl3 occurs via an initial hydrogen-atom abstraction rather than halosylation. The reductive pathway shows that the electron transfer from the ferrous-P450 species to the halogenated alkanes needs much lower barriers than the ones for chlorine abstraction in the oxidative pathway.

    20. Annulation

      Phosphane-Catalyzed [4+1] Annulation between Nitroalkenes and Morita–Baylis–Hillman Carbonates: Facile Synthesis of Isoxazoline N-Oxides by Phosphorus Ylides (pages 1183–1189)

      Dr. Rong Zhou, Chong Duan, Changjiang Yang and Prof. Dr. Zhengjie He

      Version of Record online: 27 JAN 2014 | DOI: 10.1002/asia.201301633

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      Initiation procedure: A new phosphane-catalyzed [4+1] annulation between nitroalkenes and Morita–Baylis–Hillman carbonates is reported; this provides facile and efficient synthesis of isoxazoline N-oxides (see scheme; Boc=tert-butoxycarbonyl). This reaction represents the first example of phosphorus ylide initiated [4+1] cyclization of nitroalkenes.

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