Chemistry - A European Journal

Cover image for Vol. 22 Issue 35

August 22, 2016

Volume 22, Issue 35

Pages 12201–12565

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Cover Profiles
    5. Graphical Abstract
    6. News
    7. Reviews
    8. Minireviews
    9. Communications
    10. Full Papers
    1. You have free access to this content
      Cover Picture: Unexpected Behavior of the Heaviest Halogen Astatine in the Nucleophilic Substitution of Aryliodonium Salts (Chem. Eur. J. 35/2016) (page 12201)

      Dr. François Guérard, Dr. Yong-Sok Lee, Dr. Kwamena Baidoo, Dr. Jean-François Gestin and Dr. Martin W. Brechbiel

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/chem.201602704

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      Despite 75 years having passed since its discovery, the heaviest halogen and one of the rarest of all elements, astatine, apparently still has surprises in store regarding its chemical properties. For example, astatine reactivity had been generally extrapolated from neighboring iodine, but experiments have often yielded unexpected results. In an investigation of the nucleophilic substitution of aryliodonium salts by heavy halogenides, astatine once again demonstrates novelty, with reaction kinetics being much faster than the anticipated trend within the halogen series. More information can be found in the Full Paper by F. Guérard, et al. on page 12332 ff.

    2. You have free access to this content
      Inside Cover: Assembly of Multi-Phthalocyanines on a Porphyrin Template by Fourfold Rotaxane Formation (Chem. Eur. J. 35/2016) (page 12202)

      Dr. Yasuyuki Yamada, Prof. Dr. Tatsuhisa Kato and Prof. Dr. Kentaro Tanaka

      Version of Record online: 12 AUG 2016 | DOI: 10.1002/chem.201602993

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      Self-organization of phthalocyanines has been programmed on a porphyrin template. Two phthalocyanines with four peripheral crown ether units are stacked cofacially on a porphyrin bearing four alkylammonium chains, in accordance with the number of ammonium groups on the side chain, through fourfold rotaxane formation. Significant electronic interaction is observed between the closely stacked phthalocyanines. More information can be found in the Full Paper by K. Tanaka, et al. on page 12371 ff.

    3. You have free access to this content
      Inside Back Cover: Azulenylcarbenes: Rearrangements on the C11H8 Potential Energy Surface (Chem. Eur. J. 35/2016) (page 12567)

      Dr. Stefan Henkel, Corina H. Pollok, Tim Schleif and Prof. Dr. Wolfram Sander

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/chem.201602995

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      Four of the five possible isomers of azulenylcarbenes were synthesized, isolated in low temperature matrices, and spectroscopically characterized. While 1-azulenylcarbene shows a slight preference for a singlet ground state, the other isomers have triplet ground states. The singlet—triplet splittings in azulenylcarbenes roughly parallel the π-electron densities at the various positions in the azulene rings. More information can be found in the Full Paper by W. Sander et al. on page 12479 ff.

    4. You have free access to this content
      Back Cover: Cobalt-Catalyzed C(sp2)−H Methylation by using Dicumyl Peroxide as both the Methylating Reagent and Hydrogen Acceptor (Chem. Eur. J. 35/2016) (page 12568)

      Qun Li, Yanrong Li, Weipeng Hu, Renjian Hu, Prof. Guigen Li and Hongjian Lu

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/chem.201603012

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      A cobalt-catalyzed direct methylation of the C(sp2)−H bond by using dicumyl peroxide as both the methylating reagent and hydrogen acceptor has been established. The molecule in the picture represents one of the key intermediates. The grey sphere represents the Co catalyst, which forms a Co−N bond and coordinates to the N atom of pyridine; the brown sphere represents a newly formed methyl group. The brown sphere in the phoenix's mouth (left) represents the methyl group which is used to replace a hydrogen atom in the molecule. The sphere in the mouth of the second phoenix represents the hydrogen atom which is replaced by a methyl group. More information can be found in the Communication by G. Li, H. Lu et al. on page 12286 ff.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Cover Profiles
    5. Graphical Abstract
    6. News
    7. Reviews
    8. Minireviews
    9. Communications
    10. Full Papers
    1. Frontispiece: Zwitterion/Brønsted Acid Mixtures Showing Controlled Lower Critical Solution Temperature-Type Phase Changes with Water

      Yuki Mieno, Dr. Yuki Kohno, Dr. Shohei Saita and Prof. Dr. Hiroyuki Ohno

      Version of Record online: 12 AUG 2016 | DOI: 10.1002/chem.201683561

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      Zwitterion Brønsted Acid Mixture An ammonium-type zwitterion was designed to show a lower critical solution temperature-type phase behavior with water after mixing an equimolar amount of trifluoromethanesulfonic acid, a typical Brønsted acid. This type of aqueous two-phase system affords diverse applications upon considering their combination of properties, such as thermoresponsiveness and acid functionality. Potential applications include novel catalytic reaction/product separation systems. For more details, see the Communication by H. Ohno et al. on page 12262 ff.

    2. Frontispiece: Diverse Ligand-Functionalized Mixed-Valent Hexamanganese Sandwiched Silicotungstates with Single-Molecule Magnet Behavior

      Han Xue, Prof. Dr. Jun-Wei Zhao, Rui Pan, Prof. Bai-Feng Yang, Prof. Dr. Guo-Yu Yang and Prof. Dr. Hong-Sheng Liu

      Version of Record online: 12 AUG 2016 | DOI: 10.1002/chem.201683562

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      Polyoxometalates A series of mixed-valence Mn6-sandwiched polyoxometalates (POMs) with SMM behavior have been hydrothermally made, in which the covalently functionalized Mn6 cluster via organic ligands are first observed in POMs. For more details, see the Full Paper by J.-W. Zhao, G.-Y. Yang, H.-S. Liu et al. on page 12322 ff.

  3. Cover Profiles

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Cover Profiles
    5. Graphical Abstract
    6. News
    7. Reviews
    8. Minireviews
    9. Communications
    10. Full Papers
    1. You have free access to this content
      Unexpected Behavior of the Heaviest Halogen Astatine in the Nucleophilic Substitution of Aryliodonium Salts (page 12205)

      Dr. François Guérard, Dr. Yong-Sok Lee, Dr. Kwamena Baidoo, Dr. Jean-François Gestin and Dr. Martin W. Brechbiel

      Version of Record online: 11 JUL 2016 | DOI: 10.1002/chem.201603013

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      Astatine is definitely a halogen apart.” Read more about the story behind the cover in the Cover Profile and about the research itself on page 12332 ff. (DOI: 10.1002/chem.201600922).

  4. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Cover Profiles
    5. Graphical Abstract
    6. News
    7. Reviews
    8. Minireviews
    9. Communications
    10. Full Papers
  5. News

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Cover Profiles
    5. Graphical Abstract
    6. News
    7. Reviews
    8. Minireviews
    9. Communications
    10. Full Papers
  6. Reviews

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Cover Profiles
    5. Graphical Abstract
    6. News
    7. Reviews
    8. Minireviews
    9. Communications
    10. Full Papers
    1. C=C Cleavage

      Ethenolysis: A Green Catalytic Tool to Cleave Carbon–Carbon Double Bonds (pages 12226–12244)

      Dr. Johan Bidange, Dr. Cédric Fischmeister and Dr. Christian Bruneau

      Version of Record online: 30 JUN 2016 | DOI: 10.1002/chem.201601052

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      A green C=C cleavage: Ethenolysis, which is cross-metathesis with ethylene, is a catalytic transformation that has been used to cleave internal carbon–carbon double bonds, with objectives that include the ring opening of cyclic olefins to produce dienes and the shortening of unsaturated hydrocarbon chains to degrade polymers or generate valuable shorter terminal olefins in a controlled manner.

  7. Minireviews

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Cover Profiles
    5. Graphical Abstract
    6. News
    7. Reviews
    8. Minireviews
    9. Communications
    10. Full Papers
    1. Computational Chemistry

      Computational Chemistry to the Rescue: Modern Toolboxes for the Assignment of Complex Molecules by GIAO NMR Calculations (pages 12246–12261)

      Dr. Nicolas Grimblat and Dr. Ariel M. Sarotti

      Version of Record online: 13 JUL 2016 | DOI: 10.1002/chem.201601150

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      Help! The structural and stereochemical assignment of organic compounds is often a hard and difficult task. The calculation of NMR properties of molecules using quantum chemical methods has been extensively used in the recent past to settle the tridimensional structures of complex natural and unnatural products. In this Minireview, some recent advances in this area are presented and discussed.

  8. Communications

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Cover Profiles
    5. Graphical Abstract
    6. News
    7. Reviews
    8. Minireviews
    9. Communications
    10. Full Papers
    1. Ionic Liquids

      Zwitterion/Brønsted Acid Mixtures Showing Controlled Lower Critical Solution Temperature-Type Phase Changes with Water (pages 12262–12265)

      Yuki Mieno, Dr. Yuki Kohno, Dr. Shohei Saita and Prof. Dr. Hiroyuki Ohno

      Version of Record online: 16 JUN 2016 | DOI: 10.1002/chem.201600973

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      Just a phase! Ammonium cation-based zwitterions with adequately designed hydrophobicity were mixed with aqueous Brønsted acid solutions and were shown to reversibly undergo thermoresponsive phase changes between a homogeneous mixture and liquid–liquid phase separation with water by a lower critical solution temperature-type phase transition (see figure).

    2. Pnictogens

      Synthesis of a Molecule with Four Different Adjacent Pnictogens (pages 12266–12269)

      Dr. Alexander Hinz, Prof. Dr. Axel Schulz and Dr. Alexander Villinger

      Version of Record online: 21 JUL 2016 | DOI: 10.1002/chem.201601916

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      Connect four: The synthesis and characterization of Mes*N(SbCl2)AsPMes*, a molecule containing four adjacent different pnictogens was achieved in the reaction of Li[Mes*-NAsP-Mes*] with SbCl3 (see scheme).

    3. Synthetic Methods

      Trifluoromethylthiolation and Trifluoromethylselenolation of α-Diazo Esters Catalyzed by Copper (pages 12270–12273)

      Christian Matheis, Thilo Krause, Valentina Bragoni and Prof. Dr. Lukas J. Goossen

      Version of Record online: 28 JUL 2016 | DOI: 10.1002/chem.201602730

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      Simple and effective: In the presence of catalytic amounts of copper thiocyanate, α-diazo esters are smoothly converted into the corresponding trifluoromethyl thio- or selenoethers by reaction with inexpensive, easy-to-store and handle Me4NSCF3 or Me4NSeCF3, respectively. This straightforward method gives high yields under neutral conditions at room temperature and is applicable to a wide range of functionalized molecules.

    4. Enantioselective and Regiodivergent Functionalization of N-Allylcarbamates by Mechanistically Divergent Multicatalysis (pages 12274–12277)

      Dr. Edward Richmond, Ismat Ullah Khan and Dr. Joseph Moran

      Version of Record online: 27 JUL 2016 | DOI: 10.1002/chem.201602792

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      Simple divergence: A pair of mechanistically divergent multicatalytic reaction sequences has been developed consisting of nickel-catalyzed isomerization of N-allylcarbamates and subsequent phosphoric-acid-catalyzed enantioselective functionalization of the resulting intermediates. Formal α-functionalization to give protected α-arylamines is achieved upon enantioselective Friedel–Crafts reaction with arene nucleophiles, whereas formal β-functionalization is achieved upon reaction with diarylimine electrophiles in an enantioselective Povarov-[4+2] cycloaddition.

    5. Iron Catalysis

      μ-Oxo-Dinuclear-Iron(III)-Catalyzed O-Selective Acylation of Aliphatic and Aromatic Amino Alcohols and Transesterification of Tertiary Alcohols (pages 12278–12281)

      Rikiya Horikawa, Chika Fujimoto, Dr. Ryo Yazaki and Prof. Dr. Takashi Ohshima

      Version of Record online: 28 JUL 2016 | DOI: 10.1002/chem.201602801

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      High activity for sterics: A highly chemoselective and reactive μ-oxo-dinuclear iron(III) salen catalyst for transesterification was developed. O-Selective transesterification of aromatic amino alcohols was achieved for the first time. The high activity of the iron complex enabled the use of sterically congested tertiary alcohols, including unprecedented tert-butanol.

    6. Photochemistry

      Rational Molecular Design and Synthesis of Highly Thermo- and Photostable Near-Infrared-Absorbing Heptamethine Cyanine Dyes with the Use of Fluorine Atoms (pages 12282–12285)

      Prof. Dr. Kazumasa Funabiki, Kazutaka Yagi, Masato Ueta, Mitsuru Nakajima, Masako Horiuchi, Dr. Yasuhiro Kubota and Prof. Dr. Masaki Mastui

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/chem.201602955

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      Fluorine makes it strong! Highly thermo- and photostable, near-infrared-absorbing heptamethine cyanine dyes were achieved with the use of fluorine-containing components, such as tetrakis(pentafluorophenyl)borate as a counter anion and an a N-ethyl-2,2,2-trifluoroacetamido group at the meso position (see figure).

    7. Catalysis | Hot Paper

      Cobalt-Catalyzed C(sp2)−H Methylation by using Dicumyl Peroxide as both the Methylating Reagent and Hydrogen Acceptor (pages 12286–12289)

      Qun Li, Yanrong Li, Weipeng Hu, Renjian Hu, Prof. Guigen Li and Hongjian Lu

      Version of Record online: 30 JUN 2016 | DOI: 10.1002/chem.201602445

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      C−H functionalization: A cobalt-catalyzed direct methylation of the C(sp2)−H bond by using dicumyl peroxide (DCP) as both the methylating reagent and hydrogen acceptor has been established (see scheme; acac=acetylacetone). The reaction proceeded without the use of any additives, and was proven to be applicable to various amides bearing a 2-pyridinylisopropyl (PIP) directing group.

    8. Catalysis

      One-Step Production of 1,3-Butadiene from 2,3-Butanediol Dehydration (pages 12290–12294)

      Dr. Xi Liu, Dr. Viktoria Fabos, Stuart Taylor, Prof. David W. Knight, Dr. Keith Whiston and Prof. Graham J. Hutchings

      Version of Record online: 26 JUL 2016 | DOI: 10.1002/chem.201602390

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      The direct production of 1,3-butadiene from the dehydration of 2,3-butandiol by using alumina as catalyst is reported. Under optimized kinetic reaction conditions, the production of methyl ethyl ketone and isobutyraldehyde, formed via the pinacol–pinacolone rearrangement, was markedly reduced and almost 80 % selectivity to 1,3-butadiene could be achieved. The amphoteric nature of γ-Al2O3 was identified as important and this contributed to the improved catalytic selectivity when compared with other acidic catalysts.

    9. Flow Chemistry

      A Mechanistic Investigation of the Visible-Light Photocatalytic Trifluoromethylation of Heterocycles Using CF3I in Flow (pages 12295–12300)

      Dr. Yuanhai Su, Koen P. L. Kuijpers, Niels König, Minjing Shang, Prof. Dr. Volker Hessel and Dr. Timothy Noël

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/chem.201602596

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      Precision and safety in flow: The mechanism for the visible-light-induced photocatalytic trifluoromethylation of N-methylpyrrole with CF3I has been elucidated. The use of continuous-flow microreactor technology allowed for the determination of different important parameters with high precision as well as the handling of CF3I in a straightforward manner.

    10. Supramolecular Chemistry

      Concurrent Covalent and Supramolecular Polymerization (pages 12301–12306)

      Dr. Xisen Hou, Prof. Chenfeng Ke, Dr. Yu Zhou, Dr. Zhuang Xie, Dr. Ahmed Alngadh, Dr. Denis T. Keane, Dr. Majed S. Nassar, Dr. Youssry Y. Botros, Prof. Chad A. Mirkin and Prof. J. Fraser Stoddart

      Version of Record online: 21 JUL 2016 | DOI: 10.1002/chem.201602954

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      Pushing out the polymers: A concurrent covalent and supramolecular polymerization strategy has been developed. It utilizes a rapid and efficient β-cyclodextrin-accelerated, cucurbit[6]uril-templated azide–alkyne polymerization concurrently with the supramolecular assembly of diazaperopyrenium dications, which are located periodically along the polymer backbone, by dint of π–π dimerization.

    11. Heterogeneous Catalysis

      Cooperative Catalysis for Selective Alcohol Oxidation with Molecular Oxygen (pages 12307–12311)

      Thierry K. Slot, Dr. David Eisenberg, Dylan van Noordenne, Peter Jungbacker and Prof. Dr. Gadi Rothenberg

      Version of Record online: 27 JUL 2016 | DOI: 10.1002/chem.201602964

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      Mmm…catalytic doughnuts: The combination of the oxygen reduction properties of nitrogen-doped carbons with copper- or cobalt-oxide catalysts creates cooperative catalytic regions or ′active doughnut′ sites. These sites enable selective oxidation of alcohols (e.g., cinnamyl alcohol to cinnamaldehyde) using dioxygen, with good conversion and excellent selectivity.

    12. Radical Anion Dimers

      The Tetracyanopyridinide Dimer Dianion, σ-[TCNPy]22− (pages 12312–12315)

      Dr. Jingjun Hao, Prof. Arnold L. Rheingold, Marzieh Kavand, Dr. Kipp J. van Schooten, Prof. Christoph Boehme, Dr. Marçal Capdevila-Cortada, Prof. Juan J. Novoa, Eva Wöss, Prof. Günther Knör and Prof. Joel S. Miller

      Version of Record online: 28 JUL 2016 | DOI: 10.1002/chem.201603071

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      Do or dimer: The reaction of 2,3,5,6-tetracyanopyridine (TCNPy) and Cr(C6H6)2 forms diamagnetic σ-[TCNPy]22− possessing a 1.572(3) Å intrafragment sp3–sp3 bond. This is in contrast to the structurally related 1,2,4,5-tetracyanobenzene and 1,2,4,5-tetracyanopyrazine that form π-dimer dianions possessing long, multicenter bonds.

    13. Pincer Complexes

      Divergent Coupling of Alcohols and Amines Catalyzed by Isoelectronic Hydride MnI and FeII PNP Pincer Complexes (pages 12316–12320)

      Matthias Mastalir, Mathias Glatz, Nikolaus Gorgas, Dr. Berthold Stöger, Dr. Ernst Pittenauer, Prof. Dr. Günter Allmaier, Prof. Dr. Luis F. Veiros and Prof. Dr. Karl Kirchner

      Version of Record online: 27 JUL 2016 | DOI: 10.1002/chem.201603148

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      Efficient coupling of alcohols and amines catalyzed by well-defined isoelectronic hydride MnI and FeII complexes is described. A range of alcohols and amines, including both aromatic and aliphatic substrates, was efficiently converted giving in the case of Mn selectively imines, whereas with Fe, exclusively amines were formed (see scheme).

  9. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Cover Profiles
    5. Graphical Abstract
    6. News
    7. Reviews
    8. Minireviews
    9. Communications
    10. Full Papers
    1. Cluster Compounds | Hot Paper

      Diverse Ligand-Functionalized Mixed-Valent Hexamanganese Sandwiched Silicotungstates with Single-Molecule Magnet Behavior (pages 12322–12331)

      Han Xue, Prof. Dr. Jun-Wei Zhao, Rui Pan, Prof. Bai-Feng Yang, Prof. Dr. Guo-Yu Yang and Prof. Dr. Hong-Sheng Liu

      Version of Record online: 4 JUL 2016 | DOI: 10.1002/chem.201600622

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      Organically functionalized polyoxometalates: A series of hexa-Mn-substituted sandwich-type silicotungstates was synthesized hydrothermally by replacement of the water molecules in [(B-α-SiW9O34)2MnIII4MnII2O4(H2O)4]12− organic N ligands (e.g., see figure). They are the first mixed-valent Mn6-substituted POMs covalently functionalized with organic ligands.

    2. Astatine | Hot Paper

      Unexpected Behavior of the Heaviest Halogen Astatine in the Nucleophilic Substitution of Aryliodonium Salts (pages 12332–12339)

      Dr. François Guérard, Dr. Yong-Sok Lee, Dr. Kwamena Baidoo, Dr. Jean-François Gestin and Dr. Martin W. Brechbiel

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/chem.201600922

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      Wherever I lay my At: Radiohalogenation of diaryiodonium salts has been investigated and a significantly higher reactivity of astatide has been observed. Regioselectivity and reaction kinetics can be controlled by varying the nature of substituents. The high reactivity of these precursors makes them an attractive alternative to the conventional arylstannane chemistry for radiolabeling with iodine and astatine.

    3. Alkali Metals

      Introducing a Hydrogen-Bond Donor into a Weakly Nucleophilic Brønsted Base: Alkali Metal Hexamethyldisilazides (MHMDS, M=Li, Na, K, Rb and Cs) with Ammonia (pages 12340–12346)

      Dr. Roman Neufeld, Reent Michel, Dr. Regine Herbst-Irmer, Ralf Schöne and Prof. Dr. Dietmar Stalke

      Version of Record online: 26 JUL 2016 | DOI: 10.1002/chem.201600833

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      Finally monomeric: The hitherto missing key compounds in alkali metal 1,1,1,3,3,3-hexamethyldisilazide (MHMDS) aggregation are obtained from ammonia. The monomeric trisolvated LiHMDS (see figure) and NaHMDS show unique intermolecular hydrogen bonds. The KHMDS and RbHMDS dimers are tetrasolvated, whereas the CsHMDS dimer is only disolvated, compensating with very close intra- and intermolecular Si−CH3⋅⋅⋅Cs interactions.

    4. Mineral Nucleation | Hot Paper

      Apatite Formation from Amorphous Calcium Phosphate and Mixed Amorphous Calcium Phosphate/Amorphous Calcium Carbonate (pages 12347–12357)

      Dr. Casper J. S. Ibsen, Dr. Dmitry Chernyshov and Prof. Dr. Henrik Birkedal

      Version of Record online: 27 JUL 2016 | DOI: 10.1002/chem.201601280

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      Let it grow! The kinetics of the apatite formation from hydrogen-phosphate-rich amorphous calcium phosphate with and without added carbonate is studied by a range of in situ techniques. Seeds of hydrogen-phosphate-rich apatite, akin to a few layers of octacalcium phosphate, form first and are overgrown by more stoichiometric apatite (see figure).

    5. DNA Damage

      Singlet Oxygen Attack on Guanine: Reactivity and Structural Signature within the B-DNA Helix (pages 12358–12362)

      Dr. Elise Dumont, Dr. Raymond Grüber, Emmanuelle Bignon, Prof. Christophe Morell, Dr. Juan Aranda, Dr. Jean-Luc Ravanat and Prof. Iñaki Tuñón

      Version of Record online: 21 JUL 2016 | DOI: 10.1002/chem.201601287

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      Guanine attack: Singlet oxygen attack on guanine in B-DNA with the formation of guanine endoperoxide and its subsequent intramolecular cyclization have been investigated based on QM/MM-MD simulations. The results revealed an easy stepwise mechanism and electrostatic embedding decisive to stabilizing a charge-separated intermediate (see figure).

    6. Fluorescent Probes

      Rational Design of Fluorescent Phthalazinone Derivatives for One- and Two-Photon Imaging (pages 12363–12370)

      Lingfei Yang, Dr. Yuanjun Zhu, Mengyang Shui, Tongliang Zhou, Yuanbo Cai, Wei Wang, Fengrong Xu, Yan Niu, Chao Wang, Prof. Dr. Jun-Long Zhang, Prof. Dr. Ping Xu, Dr. Lan Yuan and Prof. Dr. Lei Liang

      Version of Record online: 21 JUL 2016 | DOI: 10.1002/chem.201601499

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      Better probes by design: A pyridazinone/phthalazinone library of one- and two-photon emissive probes for use in live-cell and brain-tissue imaging (see figure) was constructed. The electronic states of the N-substituents of the pyridazinone/phthalazinone moieties effectively modulate the photophysical properties of the fluorescent probes, and the terminal groups on the alkyl chain determine the lipophilicity and subcellular organelle selectivity.

    7. Supramolecular Chemistry | Hot Paper

      Assembly of Multi-Phthalocyanines on a Porphyrin Template by Fourfold Rotaxane Formation (pages 12371–12380)

      Dr. Yasuyuki Yamada, Prof. Dr. Tatsuhisa Kato and Prof. Dr. Kentaro Tanaka

      Version of Record online: 15 JUL 2016 | DOI: 10.1002/chem.201601768

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      Four wheel drive: Fourfold rotaxane formation was utilized to synthesize a supramolecular stacked assembly in which two phthalocyanines are assembled on a porphyrin template. The close stacking leads to a significant electronic interaction between the two phthalocyanine units.

    8. Inorganic Chemistry

      Tris(2,2′-bipyridine)ruthenium Derivatives with Multiple Viologen Acceptors: Quadratic Dependence of Photocatalytic H2 Evolution Rate on the Local Concentration of the Acceptor Site (pages 12381–12390)

      Dr. Kyoji Kitamoto and Prof. Ken Sakai

      Version of Record online: 19 JUL 2016 | DOI: 10.1002/chem.201601554

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      Photo-charge separators: Single- pigment-driven multi-electron transfer in a series of novel Ru(bpy)32+ (bpy=2,2′-bipyridine) derivatives tethered to various numbers of viologen units is demonstrated to shed a new light on the molecular level control of photoinduced multi-electron transfer rate and efficiency.

    9. Enzyme Catalysis

      Unraveling the Mechanism and Regioselectivity of the B12-Dependent Reductive Dehalogenase PceA (pages 12391–12399)

      Prof.Dr. Rong-Zhen Liao, Prof.Dr. Shi-Lu Chen and Prof.Dr. Per E. M. Siegbahn

      Version of Record online: 26 JUL 2016 | DOI: 10.1002/chem.201601575

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      DFT calculations were used to understand the mechanism and regioselectivity for the cobalamin-dependent reductive dehalogenase PceA (see scheme). The CoI state initiates the heterolytic C−Cl bond cleavage in concomitant with the protonation of the substrate carbon atom. cis-Dichloroethylene was found to be the sole product in the dechlorination of trichloroethylene, which is in good agreement with the experimental finding.

    10. Luminescent Materials

      A Red-Emitting Luminescent Material Capable of Detecting Low Water Content in Organic Solvents (pages 12400–12405)

      Tianren Wang and Prof. Dr. Huanrong Li

      Version of Record online: 26 JUL 2016 | DOI: 10.1002/chem.201601616

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      Water detector: A bright red-emitting luminescent material prepared from a gel formed by simply mixing EuCl36 H2O and 4′-para-phenylcarboxyl-2,2′:6′,2′′-terpyridine in anhydrous ethanol at room temperature shows great potential in the detection of low-content water in diethyl ether and THF by means of luminescence quenching (see figure).

    11. Conformation Analysis | Hot Paper

      Cellular Cations Control Conformational Switching of Inositol Pyrophosphate Analogues (pages 12406–12414)

      Dr. Anastasia Hager, Dr. Mingxuan Wu, Dr. Huanchen Wang, Nathaniel W. Brown Jr., Prof. Stephen B. Shears, Prof. Nicolás Veiga and Prof. Dorothea Fiedler

      Version of Record online: 27 JUL 2016 | DOI: 10.1002/chem.201601754

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      Mixed messages: The inositol pyrophosphate messengers (PP-InsPs) are emerging as an important class of cellular regulators. Herein, it was shown that the PP-InsPs exhibit complex speciation behaviour and it is proposed that a unique conformational switching mechanism could contribute to their multifunctional effects (see figure).

    12. Cation Complexation

      Chiral Heteroditopic Baskets Designed from Triazolated Calixarenes and Short Peptides (pages 12415–12423)

      Alexander Gorbunov, Dr. Nadezhda Sokolova, Dr. Elena Kudryashova, Prof. Dr. Valentine Nenajdenko, Prof. Dr. Vladimir Kovalev and Dr. Ivan Vatsouro

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/chem.201601818

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      Turn ditopic! Sophisticated chiral heteroditopic hosts capable of interactions with a pair of cations may be easily prepared through CuI-catalyzed azide–alkyne cycloaddition reactions from narrow-rim propargylated calixarenes and azido-peptides. The hosts created demonstrate a direction-independent binuclear complexation, cation substitution/switching, or ordered binuclear complexation when interacting with Cu2+ and Pb2+ ions (see figure).

    13. Nanoparticles

      Importance of the Correlation between Width and Length in the Shape Analysis of Nanorods: Use of a 2D Size Plot To Probe Such a Correlation (pages 12424–12429)

      Zhihua Zhao, Zhiqin Zheng, Prof. Clément Roux, Dr. Céline Delmas, Prof. Jean-Daniel Marty, Dr. Myrtil L. Kahn and Dr. Christophe Mingotaud

      Version of Record online: 27 JUL 2016 | DOI: 10.1002/chem.201601837

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      2D or not 2D: Analysis of nanoparticle size through a simple 2D plot is used to extract the correlation between length and width in a collection or a mixture of anisotropic particles. Various electron microscopy pictures are used as examples to demonstrate the efficiency and simplicity of the proposed 2D plot combined with a multivariate analysis.

    14. Cell Imaging

      A Modular Class of Fluorescent Difluoroboranes: Synthesis, Structure, Optical Properties, Theoretical Calculations and Applications for Biological Imaging (pages 12430–12438)

      Sylvestre P. J. T. Bachollet, Dr. Daniel Volz, Béla Fiser, Stephan Münch, Dr. Franziska Rönicke, Dr. Jokin Carrillo, Harry Adams, Prof. Ute Schepers, Enrique Gómez-Bengoa, Prof. Stefan Bräse and Prof. Joseph P. A. Harrity

      Version of Record online: 28 JUL 2016 | DOI: 10.1002/chem.201601915

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      Lighting the way: A family of borylated bipyridines (BOBIPYs) fluorophores offers tunable optical properties and linker possibilities via a designed strategy of synthesis. The photophysical properties of these compounds have been measured, and the results interrogated by DFT calculations, enabling the mapping of the structure for further implementations.

    15. Chromophores

      You have full text access to this OnlineOpen article
      Highly Emissive Far Red/Near-IR Fluorophores Based on Borylated Fluorene–Benzothiadiazole Donor–Acceptor Materials (pages 12439–12448)

      Daniel L. Crossley, Dr. Inigo Vitorica-Yrezabal, Dr. Martin J. Humphries, Prof. Michael L. Turner and Dr. Michael J. Ingleson

      Version of Record online: 27 JUL 2016 | DOI: 10.1002/chem.201602010

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      The perfect couple: Cross-coupling enables the high yielding synthesis of borylated donor–acceptor materials that contain electron-rich aromatics units and/or extended effective conjugation lengths. These materials have large Stokes shifts, low LUMO energies, small band-gaps and significant fluorescence emission >700 nm in solution and in the solid state.

    16. Polymerization

      You have full text access to this OnlineOpen article
      Crystallinity Modulation of Layered Carbon Nitride for Enhanced Photocatalytic Activities (pages 12449–12454)

      Jianhai Wang, Prof. Yanfei Shen, Dr. Ying Li, Prof. Songqin Liu and Prof. Yuanjian Zhang

      Version of Record online: 20 JUL 2016 | DOI: 10.1002/chem.201602095

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      On the edge: Carbon nitride of high crystallinity and preferred orientation was successfully developed by a facile protonation of specific intermediates during conventional thermal condensation (see figure). Both the short and long lifetimes of charge carriers in the modified carbon nitride increased, which led to an increased possibility of capturing excited electrons and holes by reactive substrates in photocatalytic reactions.

    17. Catalyst Analysis | Hot Paper

      Towards an Observation of Active Conformations in Asymmetric Catalysis: Interaction-Induced Conformational Preferences of a Chiral Thiourea Model Compound (pages 12455–12463)

      Nora M. Kreienborg, Corina H. Pollok and Dr. Christian Merten

      Version of Record online: 26 JUL 2016 | DOI: 10.1002/chem.201602097

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      Good vibrations: Using vibrational circular dichroism (VCD) spectroscopy, the conformational preferences of a chiral thiourea in different solvents and its interaction with an acetate anion were investigated. Characteristic spectral signatures were found for different groups of conformers and showcase the potential of using VCD spectroscopy for studying reactant–catalyst interactions (see scheme).

    18. Inorganic Chemistry

      Donor-Appended N,C-Chelate Organoboron Compounds: Influence of Donor Strength on Photochromic Behaviour (pages 12464–12472)

      Soren K. Mellerup, Kang Yuan, Carmen Nguyen, Prof. Dr. Zheng-Hong Lu and Prof. Dr. Suning Wang

      Version of Record online: 27 JUL 2016 | DOI: 10.1002/chem.201602410

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      Let there be chelates! A series of amino-functionalized N,C-chelate organoboron compounds have been found to display bright charge-transfer luminescence and distinct photoreactivity, depending on the donor strength of the amino group and the steric effect of the aryl unit (see figure).

    19. Synthetic Methods

      Apical Functionalization of Tribenzotriquinacenes (pages 12473–12478)

      Ayan Dhara, Joshua Weinmann, Ana-Maria Krause and Dr. Florian Beuerle

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/chem.201602622

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      Reaching the top: The introduction of an alkyne moiety at the central carbon atom of the tribenzotriquinacene scaffold provides an anchor group for the facile apical functionalization of bowl-shaped molecules. Subsequent reactions, such as an azide–alkyne cycloaddition, Sonogashira cross-coupling reaction, or selective demethylation at the outer rim, were performed to highlight the synthetic potential of this approach (see picture).

    20. Photochemistry | Hot Paper

      Azulenylcarbenes: Rearrangements on the C11H8 Potential Energy Surface (pages 12479–12486)

      Dr. Stefan Henkel, Corina H. Pollok, Tim Schleif and Prof. Dr. Wolfram Sander

      Version of Record online: 12 JUL 2016 | DOI: 10.1002/chem.201601390

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      Center of attention: The spin state and the singlet–triplet splitting of the isomeric azulenylcarbenes depends on the position of the carbene center at the azulene system. 1-Azulenylcarbene has a singlet ground state, while the 2-,5- and 6-carbenes are triplet ground state molecules. The carbenes were isolated and characterized in low temperature argon matrices (see figure).

    21. Metal-Based Drugs

      Iridium(I) Compounds as Prospective Anticancer Agents: Solution Chemistry, Antiproliferative Profiles and Protein Interactions for a Series of Iridium(I) N-Heterocyclic Carbene Complexes (pages 12487–12494)

      Dr. Yvonne Gothe, Dr. Tiziano Marzo, Prof. Dr. Luigi Messori and Prof. Dr. Nils Metzler-Nolte

      Version of Record online: 22 JUL 2016 | DOI: 10.1002/chem.201601542

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      Iridium—a new player in the game: Iridium compounds in the oxidation state +I with NHC ligands show excellent antiproliferative activity against several cell lines (see figure). Mass spectrometry studies demonstrate that cellular proteins are likely targets of this new class of prospective anticancer agents.

    22. Substituent Effects

      Effect of Methyl, Hydroxyl, and Chloro Substituents in Position 3 of 3′,4′,7-Trihydroxyflavylium: Stability, Kinetics, and Thermodynamics (pages 12495–12505)

      Alfonso Alejo-Armijo, Dr. Sofía Salido, Prof. Joaquín Altarejos, Dr. A. Jorge Parola, Dr. Sandra Gago, Dr. Nuno Basílio, Dr. Luis Cabrita and Prof. Fernando Pina

      Version of Record online: 28 JUL 2016 | DOI: 10.1002/chem.201601564

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      Photochromism in 1 m HCl: Changing the substituent in position 3 of the flavylium core structure leads to dramatic changes to the thermodynamics and kinetics of the multistate molecular network (see figure). In the case of chlorine, the photochromic system operates under extremely acidic conditions.

    23. Asymmetric Synthesis | Hot Paper

      Enantioselective Syntheses of Lignin Models: An Efficient Synthesis of β-O-4 Dimers and Trimers by Using the Evans Chiral Auxiliary (pages 12506–12517)

      Dr. Costyl N. Njiojob, Prof. Joseph J. Bozell, Prof. Brian K. Long, Dr. Thomas Elder, Dr. Rebecca E. Key and Dr. William T. Hartwig

      Version of Record online: 26 JUL 2016 | DOI: 10.1002/chem.201601592

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      A model to break: Although lignin is optically inactive, its side chains present areas of local stereochemistry. However, sources of stereochemically defined lignin models are scarce. An efficient, five-step enantioselective approach to lignin model dimers and trimers is described (see scheme). The process can be scaled to multigram quantities and will provide systems to study and control the reactivity of key substructural units in lignin.

    24. Reaction Mechanism | Hot Paper

      Stereoselectivity in Autoionization Reactions of Hydrogenated Molecules by Metastable Noble Gas Atoms: The Role of Electronic Couplings (pages 12518–12526)

      Prof. Stefano Falcinelli, Prof. Marzio Rosi, Prof. Simonetta Cavalli, Prof. Fernando Pirani and Prof. Franco Vecchiocattivi

      Version of Record online: 29 JUL 2016 | DOI: 10.1002/chem.201601811

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      Beyond imagination: Analysis of total and partial ionization cross sections representative of the probability of ionic product formation in selected electronic states in Ne*-H2O, H2S, and NH3 collisions has been studied. In order to characterize the imaginary part of the optical potential, related to electronic couplings, a methodology to obtain direct information on the opacity function of these reactions has been generalized (see figure).

    25. Energetic Materials | Hot Paper

      Furazans with Azo Linkages: Stable CHNO Energetic Materials with High Densities, Highly Energetic Performance, and Low Impact and Friction Sensitivities (pages 12527–12532)

      Dr. Yanyang Qu, Dr. Qun Zeng, Prof. Jun Wang, Dr. Qing Ma, Prof. Hongzhen Li, Prof. Haibo Li and Prof. Guangcheng Yang

      Version of Record online: 21 JUL 2016 | DOI: 10.1002/chem.201601901

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      Mechanically insensitive energetic materials: Various azofurazans (see figure; Y = N or C) were prepared from the parent compound 4-amino-N′-hydroxyfurazan-3-carboximiide and their energetic properties were determined. These compounds exhibit high densities, excellent detonation properties, and relatively low impact and friction sensitivities. These properties, together with their high nitrogen contents, make them potential candidates as mechanically insensitive high explosives.

    26. Organic Polymers

      Prefunctionalized Porous Organic Polymers: Effective Supports of Surface Palladium Nanoparticles for the Enhancement of Catalytic Performances in Dehalogenation (pages 12533–12541)

      Hong Zhong, Dr. Caiping Liu, Hanghui Zhou, Yangxin Wang and Prof. Ruihu Wang

      Version of Record online: 28 JUL 2016 | DOI: 10.1002/chem.201601956

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      POP out: The introduction of carboxylate groups not only endows porous organic polymers (POPs) a superior dispersibility in H2O/EtOH, but also results in the variation of the size and location of palladium nanoparticles (NPs) from the interior pores to the external surface (see figure). Surface palladium NPs show a superior catalytic activity, stability, and recyclability in the dehalogenation of aryl halides.

    27. Synthetic Methods

      Diversification of ortho-Fused Cycloocta-2,5-dien-1-one Cores and Eight- to Six-Ring Conversion by σ Bond C−C Cleavage (pages 12542–12547)

      Lee Eccleshare, Leticia Lozada-Rodríguez, Phillippa Cooper, Dr. Laurence Burroughs, John Ritchie, Dr. William Lewis and Prof. Dr. Simon Woodward

      Version of Record online: 25 JUL 2016 | DOI: 10.1002/chem.201601970

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      Medium-ring compounds: Simple 1–3 step processes provide access to 6,n-bicyclic ring systems (n=6,8,9) and other rapidly prepared derivatives (see scheme). Several of the compounds described herein have already revealed significant activity in open-innovation drug-discovery programmes.

    28. Photocatalysis | Hot Paper

      Highly Facet-Dependent Photocatalytic Properties of Cu2O Crystals Established through the Formation of Au-Decorated Cu2O Heterostructures (pages 12548–12556)

      Guo-Zhi Yuan, Chi-Fu Hsia, Zhen-Wen Lin, Chieh Chiang, Prof. Yun-Wei Chiang and Prof. Michael H. Huang

      Version of Record online: 29 JUL 2016 | DOI: 10.1002/chem.201602173

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      Structure is the key: Whereas Au-decorated Cu2O octahedra and rhombic dodecahedra (RD) show enhanced photocatalytic activities compared to their pristine particles, small and large Au-decorated Cu2O cubes remain inactive. EPR measurements indicate a higher production of hydroxyl radicals for Cu2O rhombic dodecahedra than for octahedra upon photoirradiation, but no radicals are produced from photoirradiated Cu2O cubes (see figure).

    29. Chemical Biology

      6-Deoxyhexoses from l-Rhamnose in the Search for Inducers of the Rhamnose Operon: Synergy of Chemistry and Biotechnology (pages 12557–12565)

      Dr. Zilei Liu, Prof. Dr. Akihide Yoshihara, Dr. Ciarán Kelly, Dr. John T. Heap, Mikkel H. S. Marqvorsen, Dr. Sarah F. Jenkinson, Dr. Mark R. Wormald, Dr. José M. Otero, Dr. Amalia Estévez, Prof. Dr. Atsushi Kato, Prof. Dr. George W. J. Fleet, Prof. Dr. Ramón J. Estévez and Prof. Dr. Ken Izumori

      Version of Record online: 21 JUL 2016 | DOI: 10.1002/chem.201602482

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      Rhamnonolactone chiron perfection: The efficient production of fifteen 6-deoxy-sugars from l-rhamnose by a synergy of chemical synthesis and biotechnology to find alternative non-metabolizable inducers to rhamnose for the l-rhamnose operon is described. Several inducers with different levels of activity were identified.

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