Chemistry - A European Journal

Cover image for Vol. 23 Issue 52

Early View (Online Version of Record published before inclusion in an issue)

Editor: Neville Compton, Deputy Editors: Anne Deveson, Elisabeth Roedern

Impact Factor: 5.317

ISI Journal Citation Reports © Ranking: 2016: 29/166 (Chemistry Multidisciplinary)

Online ISSN: 1521-3765

Associated Title(s): Angewandte Chemie International Edition, Chemistry – An Asian Journal, ChemistryOpen, ChemistrySelect, ChemBioChem, ChemCatChem, ChemElectroChem, ChemMedChem, ChemPhotoChem, ChemPhysChem, ChemPlusChem, ChemSusChem, European Journal of Inorganic Chemistry, European Journal of Organic Chemistry

  1. Full Papers

    1. Cancer Therapeutics | Hot Paper

      Encapsulating pH-Responsive Doxorubicin–Phthalocyanine Conjugates in Mesoporous Silica Nanoparticles for Combined Photodynamic Therapy and Controlled Chemotherapy

      Roy C. H. Wong, Prof. Dennis K. P. Ng, Prof. Wing-Ping Fong and Prof. Pui-Chi Lo

      Version of Record online: 19 SEP 2017 | DOI: 10.1002/chem.201703188

      Thumbnail image of graphical abstract

      Photodynamic duo: Doxorubicin (Dox) was conjugated to a zinc(II) phthalocyanine (ZnPc) and then anchored to mesoporous silica. The chemocytotoxic Dox released under acidic conditions together with singlet oxygen generated upon irradiation on the encapsulated ZnPc could kill cancer cells effectively. The nanoparticles function as both nanophotosensitizers for photodynamic therapy and as nanoplatforms for pH-controlled drug release.

    2. Chromophores

      An Unprecedented Blue Chromophore Found in Nature using a “Chemistry First” and Molecular Networking Approach: Discovery of Dactylocyanines A–H

      Dr. Natacha Bonneau, Guanming Chen, Dr. David Lachkar, Dr. Asmaa Boufridi, Jean-François Gallard, Dr. Pascal Retailleau, Dr. Sylvain Petek, Dr. Cécile Debitus, Dr. Laurent Evanno, Dr. Mehdi A. Beniddir and Prof. Dr. Erwan Poupon

      Version of Record online: 19 SEP 2017 | DOI: 10.1002/chem.201702336

      Thumbnail image of graphical abstract

      Blue-eyed meroterpenes: Guided by a “chemistry first” approach using molecular networking, eight new bright-blue-colored natural compounds, namely dactylocyanines A–H bearing a zwitterionic quinonoid chromophore, were isolated from the Polynesian marine sponge Dactylospongia metachromia.

  2. Communications

    1. Ruthenium Catalysis

      Mild N-Alkylation of Amines with Alcohols Catalyzed by the Acetate Ru(OAc)2(CO)(DiPPF) Complex

      Dr. Rosario Figliolia, Dr. Salvatore Baldino, Dr. Hans G. Nedden, Dr. Antonio Zanotti-Gerosa and Prof. Walter Baratta

      Version of Record online: 19 SEP 2017 | DOI: 10.1002/chem.201702996

      Thumbnail image of graphical abstract

      Amico rutenio: The complex Ru(OAc)2(CO)(DiPPF), easily prepared by carbonylation of Ru(OAc)2(DiPPF) with H2CO, efficiently catalyzes the alkylation of primary and secondary amines with alcohols under mild reaction conditions. Addition of a suitable amount of trifluoroacetic acid increases the rate of reaction. Evidence of the formation of the monohydride RuH(OAc)(CO)(DiPPF) species is provided.

    2. Supramolecular Chemistry

      Gold(I) Metallo-Tweezers for the Recognition of Functionalized Polycyclic Aromatic Hydrocarbons by Combined π–π Stacking and H-Bonding

      Chiara Biz, Dr. Susana Ibáñez, Dr. Macarena Poyatos, Prof. Dmitry Gusev and Prof. Eduardo Peris

      Version of Record online: 19 SEP 2017 | DOI: 10.1002/chem.201703984

      Thumbnail image of graphical abstract

      Easy-tweezy: The presence of pyrene tags at the NHC ligands and the N−H group of a carbazole linker enables AuI tweezers to bind polyaromatic guests through combined π-stacking and H-bonding.

  3. Full Papers

    1. Coordination Chemistry | Hot Paper

      The Stepwise Reaction of Rhodium and Iridium Complexes of Formula [MCl24C,N,N′,P−L)] with Silver Cations: A Case of trans-Influence and Chiral Self-Recognition

      María Carmona, Leyre Tejedor, Dr. Ricardo Rodríguez, Dr. Vincenzo Passarelli, Prof. Dr. Fernando J. Lahoz, Dr. Pilar García-Orduña and Prof. Dr. Daniel Carmona

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201702711

      Thumbnail image of graphical abstract

      Let's go step by step: The chlorido ligands in complexes [MCl24C,N,N′,PL)] (M=Rh, Ir) were sequentially removed to give bis-solvato complexes of formula [M(κ4C,N,N′,PL)(NCMe)2]2+. The involved mono-, di- and trimetallic intermediates were isolated and characterized. The formation of these intermediates takes place with chiral self-recognition. The stereochemistry determined for the new species is compatible with the retention of the configuration of the metallic fragments throughout the whole process.

  4. Communications

    1. Synthetic Methods

      Helical Threads: Enantiomerically Pure Carbo[6]Helicene Oligomers

      Cédric Schaack, Eric Sidler, Dr. Nils Trapp and Prof. Dr. François Diederich

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703024

      Thumbnail image of graphical abstract

      Bigger, better! An efficient route to enantiopure 2,15-dialkynylated carbo[6]helicenes and buta-1,3-diyne-1,4-diyl- and thiene-2,5-diyl-linked dimeric and tetrameric oligomers is described. The chiroptical properties are correlated with the extent of π-electron delocalization. X-ray analysis provided conformational information consistent with DFT-calculated structures. The thiene-2,5-diyl-bridged dimers display intense fluorescence emission, which is a rare property in carbohelicene chemistry (see scheme).

  5. Full Papers

    1. Theoretical Chemistry

      Bonding in Heavier Group 14 Zero-Valent Complexes—A Combined Maximum Probability Domain and Valence Bond Theory Approach

      Dr. Jan Turek, Dr. Benoît Braïda and Prof. Frank De Proft

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703053

      Thumbnail image of graphical abstract

      Zero-valent complexes: Heavier Group 14 zero-valent complexes, the “tetrylones”, are investigated by combining valence bond (VB) theory and maximum probability domain (MPD) approaches. As confirmed by both VB and MPB, the bonding in the studied E0 (E=Si, Ge, Sn and Pb) compounds is best described as a resonating combination of “ylidone” and “ylidene” structures with a minor contribution of the “bent allene” structure. Moreover, the VB calculations allow for a straightforward assessment of the π-backbonding stabilization energy.

    2. Luminophores

      Germanium-Bridged 2-Phenylbenzoheteroles as Luminophores Exhibiting Highly Efficient Solid-State Fluorescence

      Prof. Dr. Masaki Shimizu, Daiki Ryuse and Takumi Kinoshita

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703235

      Thumbnail image of graphical abstract

      Germanium bridges: Adding a Ge bridge on 2-phenylbenzoheteroles is found to be effective as a new molecular design principle for organic luminophores that exhibit highly efficient solid-state fluorescence. It is found that [1]benzogermolo[3,2-b]indole, -benzofuran, and -thiophene-S,S-dioxide emit violet-to-blue light with good-to-high quantum yields in powder form, demonstrating the high potential of such bilaterally unsymmetrical germylene-bridged biaryls as solid-state light-emitting materials (see scheme).

    3. Dyes/Pigments

      Locally Excited State–Charge Transfer State Coupled Dyes as Optically Responsive Neuron Firing Probes

      Dr. Dumitru Sirbu, Dr. John B. Butcher, Dr. Paul G. Waddell, Prof. Peter Andras and Prof. Andrew C. Benniston

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703366

      Thumbnail image of graphical abstract

      Rhythm of the Light: Extended donor–acceptor BODIPY derivatives were examined as new optical neuron probes. The dyes were tested by recording the activity of neurons in the stomatogastric ganglion (STG) of the brown crab Cancer pagurus. A simple structure reactivity relationship was derived.

  6. Communications

    1. Metallacycles

      Titanocene Silylpropyne Complexes: Promising Intermediates en route to a Four-Membered 1-Metallacyclobuta-2,3-diene?

      Dr. Fabian Reiß, Dr. Melanie Reiß, Dr. Anke Spannenberg, Dr. Haijun Jiao, Dr. Dirk Hollmann, Dr. Perdita Arndt, Prof. Dr. Uwe Rosenthal and Dr. Torsten Beweries

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703444

      Thumbnail image of graphical abstract

      Rings of titan: The reaction of alkyl substituted alkynes Me3SiC2CH2R (1: R=SiMe3; 2: R=N(SiMe3)2) with Cp′2TiCl2 (Cp′=Cp, Cp*) and Mg yields three stable alkyne complexes or the unusual Cp*2Ti(III)(η3-Me3SiC2CH2) η3-propargyl complex.

  7. Full Papers

    1. Carbonyl ligands

      From an Easily Accessible Pentacarbonylcobalt(I) Salt to Piano Stool Cations [(arene)Co(CO)2]+

      Stefan C. Meier, Albina Holz, Alexei Schmidt, Dr. Daniel Kratzert, Dr. Daniel Himmel and Prof. Dr. Ingo Krossing

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703589

      Thumbnail image of graphical abstract

      Metal carbonyl cations go organic: The facile preparation of [Co(CO)5]+, stabilized by the weakly coordinating anion [Al(ORF)4]- {RF=C(CF3)3}, works without superacids in the organic solvent ortho-difluorobenzene (C6H4F2). The salt can be easily isolated on a multigram scale and used for further CoI chemistry, for example, the preparation of the hitherto unknown cationic two-legged piano-stool carbonyl complexes [(arene)Co(CO)2]+ (arene=C6H5CH3, C6H6, C6H5F, and C6H4F2).

  8. Communications

    1. Photoredox Catalysis

      Organo-Photoredox Catalyzed Oxidative Dehydrogenation of N-Heterocycles

      Manoj K. Sahoo, Garima Jaiswal, Jagannath Rana and Prof. Dr. Ekambaram Balaraman

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703642

      Thumbnail image of graphical abstract

      Promoting hetero-aromaticity: We report a room temperature oxidative dehydrogenation of N-heterocycles to N-hetero-aromatics. This unified strategy has been achieved by a metal-free visible-light photoredox catalyst in air under base and additive-free conditions. The broad substrate scope, high functional group tolerance, and simplicity of the reaction make this process more attractive towards the effective synthesis of a wide range of important N-hetero-aromatic commodities such as quinoline, quinoxaline, quinazoline, acridine, and indole.

    2. Gas-Phase Reactions

      On the Electronic Origin of Remarkable Ligand Effects on the Reactivities of [NiL]+ Complexes (L=C6H5, C5H4N, CN) towards Methane

      Dr. Shaodong Zhou, Marjan Firouzbakht, Dr. Maria Schlangen, Prof. Dr. Martin Kaupp and Prof. Dr. Helmut Schwarz

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703767

      Thumbnail image of graphical abstract

      The gas-phase reactions of [Ni(C6H5)]+, [Ni(C5H4N)]+, and [Ni(CN)]+ with methane have been investigated both experimentally and computationally. Whereas [Ni(C6H5)]+ exclusively abstracts one hydrogen atom from methane, [Ni(CN)]+ brings about both H-atom abstraction and the ligand exchange to release HCN; in contrast, [Ni(C5H4N)]+ is inert towards this substrate under the same conditions.

    3. Synthetic Methods

      Chemoselective Reduction of Phosphine Oxides by 1,3-Diphenyl-Disiloxane

      Joseph A. Buonomo, Carter G. Eiden and Dr. Courtney C. Aldrich

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703875

      Thumbnail image of graphical abstract

      Simple and clean: We report the discovery of the most powerful chemoselective reductant for the reduction of phosphine oxides to the corresponding phosphines to date, 1,3-diphenyl-disiloxane (DPDS). DPDS could be deployed alone to afford high yields of phosphines from secondary and tertiary phosphine oxides very rapidly or used in tandem with the Brønsted acid bis-(p-nitrophenyl)phosphoric acid (BNPA) in reductions of acyclic phosphine oxides at ambient temperature.

  9. Cover Pictures

    1. You have free access to this content
      Photo-Induced Assembly of a Luminescent Tetraruthenium Square

      Baptiste Laramée-Milette, Dr. Francesco Nastasi, Dr. Fausto Puntoriero, Prof. Dr. Sebastiano Campagna and Prof. Dr. Garry S. Hanan

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703878

      Thumbnail image of graphical abstract

      Self-assembly is a powerful synthetic tool that has led to the development of one-, two- and three-dimensional architectures. Herein a strategy for the construction and de-construction of a supramolecular structure through light-induced assembly and dis-assembly is described. These results open the way to a new avenue in supramolecular chemistry, leading to the preparation of structurally-organized assemblies by photochemical techniques. More information can be found in the Full Paper by G. S. Hanan et al. (DOI: 10.1002/chem.201702714).

    2. You have free access to this content
      Encapsulating pH-Responsive Doxorubicin–Phthalocyanine Conjugates in Mesoporous Silica Nanoparticles for Combined Photodynamic Therapy and Controlled Chemotherapy

      Roy C. H. Wong, Prof. Dennis K. P. Ng, Prof. Wing-Ping Fong and Prof. Pui-Chi Lo

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201704058

      Thumbnail image of graphical abstract

      Zinc(II) phthalocyanine (ZnPc) was conjugated with doxorubicin (Dox) through an acid-cleavable hydrazone linker, and the resulting conjugate was encapsulated into mesoporous silica nanoparticles. Upon internalization into cancer cells, Dox was released after acidic cleavage of the hydrazone linker. The synergistic effect of the chemocytotoxic agent and the singlet oxygen generated upon irradiation of the encapsulated ZnPc killed the cells efficiently. These nanoparticles thus exhibit dual functionality as nanophotosensitizers for photodynamic therapy and as nanoplatforms for pH-controlled drug release. More information can be found in the Full Paper by D. K. P. Ng, P.-C. Lo et al. (DOI: 10.1002/chem.201703188).

    3. You have free access to this content
      Kinetic Studies on Formic Acid Dehydrogenation Catalyzed by an Iridium Complex towards Insights into the Catalytic Mechanism of High-Pressure Hydrogen Gas Production

      Dr. Masayuki Iguchi, Dr. Heng Zhong, Dr. Yuichiro Himeda and Prof. Dr. Hajime Kawanami

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201704083

      Thumbnail image of graphical abstract

      Kinetic studies of the reaction mechanism of formic acid (FA) dehydrogenation under high-pressure conditions were investigated in the presence of iridium complex with 4,4’-dihydroxy-2,2’-bipyridine ligand. Kinetic isotope effect experiments revealed that the shift of the rate-limiting step at low and high concentrations of FA can be caused by the pH dependence of the reaction steps. The proposed equation corresponds well to the results of the shift phenomena. The results should be useful for designing hydrogen-fuel-filling systems in the near future. More information can be found in the Full Paper by H. Kawanami et al. (DOI: 10.1002/chem.201702969).

    4. You have free access to this content
      Coordination Behavior of a Planar Chiral Cyclic (Amino)(Ferrocenyl)Carbene Ligand in Iridium Complexes

      Yuta Shikata, Risa Yasue and Prof. Kazuhiro Yoshida

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201704199

      Thumbnail image of graphical abstract

      Owing to their unique electronic properties, N-heterocyclic carbenes (NHCs) have attracted much attention as powerful ligands in transition-metal catalysis. However, the development of effective chiral NHCs remains a challenge, as the flat heterocyclic structures typically used are challenging to design. Herein, coordination behavior of a new chiral NHC, cyclic (amino)(ferrocenyl)carbene (CAFeC), was examined. Full characterization of its iridium complexes revealed that CAFeC has a strong coordination ability, surpassing that of classic NHC ligands, as well as a promising planar chiral environment. These fundamental data are expected to further advance the development of CAFeC ligands. More information can be found in the Full Paper by Y. Shikata, R. Yasue, and K. Yoshida (DOI: 10.1002/chem.201703467).

    5. You have free access to this content
      The 1,6,7,12-Tetraazaperylene Bridging Ligand as an Electron Reservoir and Its Disulfonato Derivative as Redox Mediator in an Enzyme–Electrode Process

      Dr. Thomas Brietzke, Thomas Dietz, Alexandra Kelling, Prof. Uwe Schilde, Julianae Bois, Dr. Harald Kelm, Manuel Reh, Dr. Markus Schmitz, Prof. Thomas Körzdörfer, Prof. Silke Leimkühler, Prof. Ulla Wollenberger, Prof. Hans-Jörg Krüger and Prof. Hans-Jürgen Holdt

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201704226

      Thumbnail image of graphical abstract

      Complex dication [{Ru(L-N4Me2)}2{μ-tape-(SO3)2}]2+ ([4]2+) was exploited as a redox mediator between an anaerobic homogenous reaction solution of an enzyme system (sulfite/sulfite oxidase) and the electrode by participation of the low-energy π*-orbital of the disulfonato-substituted bridging ligand tape–(SO3)22−. Tape diruthenium complexes could be a new valuable group of artificial redox mediators. The redox potential of these complexes can be easily modified for the required purpose by different substituents at the bridging tape and the terminal macrocycle. More information can be found in the Communication by H.-J. Krüger, H.-J. Holdt et al. (DOI: 10.1002/chem.201703639).

  10. Full Papers

    1. Enantioselective Synthesis

      Design and Synthesis of Chiral Diene Ligands for RhI-Catalyzed Enantioselective Arylation of N-DPP-protected Aldimines: Synthesis of the Antifungal Agent Bifonazole

      Jin-Fong Syu, Huang-Ying Lin, Yu-Yi Cheng, Yao-Chu Tsai, Yi-Ching Ting, Ting-Shen Kuo, Dr. Damodar Janmanchi, Dr. Ping-Yu Wu, Dr. Julian P. Henschke and Prof. Dr. Hsyueh-Liang Wu

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201702509

      Thumbnail image of graphical abstract

      Cyclo-somatic: The design, synthesis and testing of a novel set of chiral diene ligands bearing amido groups for the highly enantioselective 1,2-arylation reactions of N-diphenylphosphinyl-protected aldimines is described. In the presence of 3 mol % of the chiral RhI/L4 ad catalyst at 60 °C in dioxane, the corresponding addition products were isolated in yields between 31–99 % in 91–99 % ee.

  11. Minireviews

    1. Supramolecular Chemistry

      Aromatic Micelles as a New Class of Aqueous Molecular Flasks

      Dr. Kei Kondo, Dr. Jeremy K. Klosterman and Dr. Michito Yoshizawa

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201702519

      Thumbnail image of graphical abstract

      Adaptable nanocontainers: Micelles are the oldest class of supramolecules and are typically composed of amphiphilic molecules with aliphatic subunits. This Minireview focuses on the recent development of micellar nanostructures formed from amphiphiles with oligoarylene or polyaromatic frameworks. The new aromatic micelles providing polyaromatic shells display superior binding capabilities toward medium to large molecules in water.

  12. Full Papers

    1. Supramolecular Chemistry | Hot Paper

      Photo-Induced Assembly of a Luminescent Tetraruthenium Square

      Baptiste Laramée-Milette, Dr. Francesco Nastasi, Dr. Fausto Puntoriero, Prof. Dr. Sebastiano Campagna and Prof. Dr. Garry S. Hanan

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201702714

      Thumbnail image of graphical abstract

      Lit up like Times Square: The first photo-induced assembly of a metallosupramolecular square exhibits high quantum yield and long excited-state lifetimes.

    2. Liquid Crystals

      You have full text access to this OnlineOpen article
      Rational Design of Rod-Like Liquid Crystals Exhibiting Two Nematic Phases

      Dr. Richard J. Mandle, Dr. Stephen J. Cowling and Prof. John W. Goodby

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201702742

      Thumbnail image of graphical abstract

      Soft matter: Structure–property relationship for the recently discovered nematic-to-nematic phase transition exhibited by rod-like liquid crystals, allowing these materials to be accessed by rational design rather than serendipity, is reported (see scheme).

    3. Manganese | Hot Paper

      Robust Macroscopic 3D Sponges of Manganese Oxide Molecular Sieves

      Dr. Zhenxin Liu, Depeng Wu, Xuehui Guo, Prof. Dr. Shaoming Fang, Prof. Dr. Lizhen Wang, Prof. Dr. Yu Xing and Prof. Dr. Steven L. Suib

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201702787

      Thumbnail image of graphical abstract

      Suck it up: Free-standing 3D OMS-2 sponges with various densities were developed and demonstrated outstanding features, including good mechanical properties, facile preparation, high electrical conductivity, high porosity, permeability, recyclability, as well as selective water absorption in preference to oil. Some of these properties exhibit systematic trends with various densities.

  13. Communications

    1. Supramolecular chemistry | Hot Paper

      Anion-Functionalized Pillararenes for Efficient Sulfur Dioxide Capture: Significant Effect of the Anion and the Cavity

      Wenjun Lin, Xiuyuan Zhou, Jingsong Cai, Kaihong Chen, Xi He, Xueqian Kong, Prof. Haoran Li and Prof. Congmin Wang

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703007

      Thumbnail image of graphical abstract

      Catch me! A series of anion-functionalized pillararenes were prepared and applied in the capture of SO2, which exhibited high SO2 capacity and excellent reversibility, where SO2 chemical absorption was strenghened significantly by the cavity.

  14. Full Papers

    1. Ligand Effects

      Cyclopalladation in the Periphery of a NHC Ligand as the Crucial Step in the Synthesis of Highly Active Suzuki–Miyaura Cross-Coupling Catalysts

      Dr. Agnes Fizia, Dr. Maximilian Gaffga, Dr. Johannes Lang, Dr. Yu Sun, Prof. Dr. Gereon Niedner-Schatteburg and Prof. Dr. Werner R. Thiel

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201702877

      Thumbnail image of graphical abstract

      Coordination matters! Two different modes of coordinating an aminopyrimidine to the palladium site of C−C coupling catalysts gives rise to very different reactivities (see figure).

    2. Catalysis | Hot Paper

      Ligand Influence on Carbonyl Hydroboration Catalysis by Alkali Metal Hydridotriphenylborates [(L)M][HBPh3] (M=Li, Na, K)

      Hassan Osseili, Dr. Debabrata Mukherjee, Dr. Thomas P. Spaniol and Prof. Dr. Jun Okuda

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201702818

      Thumbnail image of graphical abstract

      Light metal: Comparison of ligands (L) on the catalytic carbonyl hydroboration by [(L)M][HBPh3] (M=Li, Na, K) confirms the unique combination of Me6TREN and lithium for high activity.

    3. Electrocatalysis

      Effect of Carbon Supports on Enhancing Mass Kinetic Current Density of Fe-N/C Electrocatalysts

      Xinghua Chen, Fei He, Prof.Dr. Yanfei Shen, Yiran Yang, Hao Mei, Prof.Dr. Songqin Liu, Prof.Dr. Toshiyuki Mori and Prof.Dr. Yuanjian Zhang

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703020

      Thumbnail image of graphical abstract

      Interface effect: A study into the intrinsic role of carbon supports for Fe-N/C alternatives to Pt/C catalysts for oxygen reduction in fuel cells revealed that when immobilized on suitable support, the Fe−N/C demonstrated an improved mass JK that was comparable to that of Pt/C and higher than most reported M−N/C catalysts (see scheme).

  15. Communications

    1. Cluster Compounds | Hot Paper

      Bridging Coordination of Vinylarenes to Pd3- or Pd4 Cluster Sites

      Dr. Yuki Ishikawa, Seita Kimura, Dr. Koji Yamamoto and Prof. Tetsuro Murahashi

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703023

      Thumbnail image of graphical abstract

      Pd and arene coordination: It was proved that a Pd3- or Pd4 sheet cluster accommodates vinylarenes at its bridging coordination site in an unusual mode in palladium chemistry. The arene coordination precedes olefin coordination at the Pd3 site, and oxidative π-addition takes place at the Pd4 site.

  16. Full Papers

    1. Stimuli-Responsive Materials | Hot Paper

      Autonomous and Continuous Stimuli-Responsive Polymer Surface for Antibacterial Application through Enzymatic Self-Propagating Reactions

      Chao Ding, Zhengqing Yan, Prof. Jinsong Ren and Prof. Xiaogang Qu

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703067

      Thumbnail image of graphical abstract

      Please respond! pH-Responsive polymer surfaces that are capable of transforming specific local fleeting stimuli into global macroscopic property changes were designed by the introduction of self-propagating reactions into polymer-surface systems (see figure). The H+-responsive polymer surfaces can be employed for antibacterial applications, and this design strategy offers methods for achieving autonomously reconfigurable materials.

    2. Supramolecular Chemistry | Hot Paper

      Molecular Switching in Confined Spaces: Effects of Encapsulating the DHA/VHF Photo-Switch in Cucurbiturils

      Dr. Michael Å. Petersen, Dr. Brian Rasmussen, Nicolaj N. Andersen, Prof. Stephan P. A. Sauer, Prof. Mogens Brøndsted Nielsen, Prof. Sophie R. Beeren and Prof. Michael Pittelkow

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703196

      Thumbnail image of graphical abstract

      Switches in water: The dihydroazulene/vinylheptafulvene (DHA/VHF) photo-switching behavior in water is strongly influenced by supramolecular interactions with a series of cucurbit[n]uril (CB) host molecules. In CB7 inclusion complexes, the kinetics of the thermal VHF-to-DHA back-reaction is accelerated, while in CB8 inclusion complexes, the kinetics is slowed down as compared to the free photo-switch.

  17. Reviews

    1. Redox Devices

      Viologens and Their Application as Functional Materials

      Laura Striepe and Prof. Dr. Thomas Baumgartner

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703348

      Thumbnail image of graphical abstract

      Organic functional materials: Viologens have recently been rediscovered due to their multifaceted utility for practical applications. This Review focuses on current progress of electrochromic devices, molecular machines and various organic batteries, and how viologens, as an organic material, are an upcoming competitor to conventional metal-based technologies.

  18. Full Papers

    1. Photovoltaics

      Incorporating an Inert Polymer into the Interlayer Passivates Surface Defects in Methylammonium Lead Halide Perovskite Solar Cells

      Dr. Shiqing Bi, Xuning Zhang, Liang Qin, Rong Wang, Jiyu Zhou, Xuanye Leng, Xiaohui Qiu, Yuan Zhang, Prof. Huiqiong Zhou and Prof. Zhiyong Tang

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703382

      Thumbnail image of graphical abstract

      Danger danger! High voltage! Incorporating the inert PMMA into the fullerene based electron extraction layer not only suppresses unfavorable hysteresis in perovskite solar cells but also enhances the device stability. The improvements can be primarily ascribed to surface passivation with the functional groups in PMMA and the formation of a more compact and dense layer together with PCBM to improve protection of perovskite films.

    2. Chirality

      Possible Case of Halogen Bond-Driven Self-Disproportionation of Enantiomers (SDE) via Achiral Chromatography

      Shumpei Terada, Motohiro Hirai, Ayaka Honzawa, Prof. Osamu Kitagawa, Angelika Kamizela, Alicja Wzorek and Prof. Vadim A. Soloshonok

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703308

      Thumbnail image of graphical abstract

      Enriched by chromatography: The remarkably high magnitude of the self-disproportionation of enantiomers (SDE) phenomenon via achiral chromatography (MPLC, gravity column), observed for axially chiral mebroqualone derivatives, is caused by the formation of intermolecular halogen bonds (C=O−Br). This strong halogen bonding gives a clear preference for heterochiral high-order species, allowing for practical preparation of enantiomerically enriched (up to >99 % ee) and depleted (up to <11 % ee) material via achiral chromatography.

    3. Enantiodifferentiation

      Polyaspartates as Thermoresponsive Enantiodifferentiating Helically Chiral Alignment Media for Anisotropic NMR Spectroscopy

      Mira Schwab, Dominik Herold and Prof. Dr. Christina M. Thiele

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201702884

      Thumbnail image of graphical abstract

      Hot and cool RDCs: Herein we present poly-β-phenethylaspartates as new helically chiral enantiodifferentiating alignment media which undergo a temperature induced helix reversal. This allows the measurement of residual dipolar couplings in two different helix conformations (P- and M-helix) within the same sample.

    4. Water Splitting

      Novel 3D Semiconducting Open-Frameworks based on Cuprous Bromides with Visible Light Driven Photocatalytic Properties

      Prof. Xiao-Wu Lei, Cheng-Yang Yue, Jun-Chao Wei, Rui-Qing Li, Fu-Qi Mi, Yan Li, Lu Gao and Quan-Xiu Liu

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201702736

      Thumbnail image of graphical abstract

      Using the well-known photosensitive metal-complexes [TM(2,2-bipy)3]2+ as templates, a special three-dimensional metal halogenide framework of [TM(2,2-bipy)3]Cu4Br6 was designed. These microporous materials feature tunable narrow band gaps and stable visible light driven photocatalytic properties including hydrogen evolution from water splitting and photodegradation of organic pollutants, mainly arising from the multi-electronic effects of TM complex templates and host framework. This technique facilitates the integration of crystalline microporous materials and semiconducting photocatalytic properties into one d10 transition metal halogenide for the first time.

    5. Metallacycles

      Chiral Sulfur Functional Groups as Definers of the Chirality at the Metal in Ir and Rh Half-Sandwich Complexes: A Combined CD/X-ray Study

      Marta G. Avello, María Frutos, María C. de la Torre, Alma Viso, Marina Velado, Roberto Fernández de la Pradilla, Miguel A. Sierra, Heinz Gornitzka and Catherine Hemmert

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201702662

      Thumbnail image of graphical abstract

      Enantioenriched metallacycles: Enantiopure chiral-at-metal IrIII and RhIII half-sandwich complexes are produced from mesoionic carbenes (MICs) that contain chiral sulfoxide or sulfoximine functional groups. The synthetic sequence of MIC complexation/C−H aromatic activation efficiently affords enantiopure five-membered metallacycles. The configuration at the metal center remains unaltered during the formation of the cationic IrIII complexes and the insertion of alkynes, as demonstrated by a combined circular dichroism/X-ray study.

    6. Zeolites | Hot Paper

      Embedded Isoreticular Zeolites: Concept and Beyond

      Jung Cho, Hyun June Choi, Prof. Dr. Peng Guo, Dr. Jiho Shin, Prof. Dr. Xiaodong Zou and Prof. Dr. Suk Bong Hong

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201702417

      Thumbnail image of graphical abstract

      Defining embedded isoreticular zeolites: The definition and concept of embedded isoreticular zeolites can uncover a whole series of related structures (see figure) with similar structural properties and provide insight into their rational synthesis.

    7. Molecular Geometry

      Dissecting Trichalcogenasumanenes: π-Bowl to Planar, Invertible Curvature, and Chiral Polycycles

      Xueqing Hou, Xuexiang Li, Chunlin Sun, Lichuan Chen, Yantao Sun, Zhe Liu, Prof. Dr. Hao-Li Zhang and Prof. Dr. Xiangfeng Shao

      Version of Record online: 18 SEP 2017 | DOI: 10.1002/chem.201703469

      Thumbnail image of graphical abstract

      Forceps stat! Performing surgery on hetero-buckybowl trichalcogenasumanene gives the [7-5-6]-fused, [7-6-6]-fused, and [7-7-6]-fused polycycles, and results in the gradual conversion of the molecular geometry from π-bowl to chiral polycycle.

    8. Nonlinear optics

      Optical Limiting Properties of 3,5-Dithienylenevinylene BODIPY Dyes at 532 nm

      Jessica Harris, Dr. Lizhi Gai, Gugu Kubheka, Dr. John Mack, Prof. Tebello Nyokong and Prof. Zhen Shen

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201702503

      Thumbnail image of graphical abstract

      BODIPYs as optical limiters: The optical limiting properties of a series of 3,5-dithienylenevinylene BODIPY dyes with D-π-A type structures were studied by using the z-scan technique at 532 nm in the nanosecond pulse range. An unusually strong reverse saturable absorption response was observed when the compounds are embedded in poly(bisphenol carbonate A) polymer thin films.

  19. Communications

    1. Radiochemistry | Hot Paper

      Dual-Nuclide Radiopharmaceuticals for Positron Emission Tomography Based Dosimetry in Radiotherapy

      Alexander Wurzer, Dr. Christof Seidl, Dr. Alfred Morgenstern, Dr. Frank Bruchertseifer, Prof. Dr. Markus Schwaiger, Prof. Dr. Hans-Jürgen Wester and Dr. Johannes Notni

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201702335

      Thumbnail image of graphical abstract

      Take two: Dual-nuclide labeled radiopharmaceuticals with therapeutic and PET functionality, derived from common and widely available metal radionuclides, enable a precise PET-based dosimetry for improvement of individual therapeutic outcome and increased patient safety in molecular radiotherapy.

  20. Concepts

    1. Polymers

      Synthesis of Ladder Polymers: Developments, Challenges, and Opportunities

      Yew Chin Teo, Holden W. H. Lai and Prof. Dr. Yan Xia

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201702219

      Thumbnail image of graphical abstract

      Climbing ladders: Rigid ladder polymers represent an uncommon but intriguing type of polymer architecture consisting of continuously fused rings in their backbones with highly restricted bond rotations. Their unique macromolecular structures lead to unusual and interesting properties. We highlight the synthetic approaches towards non-conjugated and conjugated ladder polymers to elucidate their historical development. We also present challenges and perspectives on the synthesis and understanding of such unconventional rigid polymers.

  21. Full Papers

    1. Asymmetric Catalysis

      Selecting Chiral BINOL-Derived Phosphoric Acid Catalysts: General Model To Identify Steric Features Essential for Enantioselectivity

      Jolene P. Reid and Prof. Jonathan M. Goodman

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201702019

      Thumbnail image of graphical abstract

      How to choose a cat: A general model to guide the best choice of phosphoric acid catalyst for nucleophilic addition to imines has been developed. These rules are consistent for seventy-seven papers containing over 1000 examples, explaining enantioselectivity trends with varying 3,3′ group and correctively identifying steric features essential for efficient stereoinduction.

    2. Nanotheranostics | Hot Paper

      MnAl Layered Double Hydroxide Nanoparticles as a Dual-Functional Platform for Magnetic Resonance Imaging and siRNA Delivery

      Dr. Huali Zuo, Weiyu Chen, Bei Li, Kewei Xu, Dr. Helen Cooper, Dr. Zi Gu and Prof. Dr. Zhi Ping Xu

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201702835

      Thumbnail image of graphical abstract

      Multifunctional nanoparticles: Dual-functional manganese-based layered double hydroxide nanoparticles (Mn-LDH) were fabricated by a co-precipitation method. Their pH-sensitive behaviour significantly enhanced T1-weighted magnetic resonance imaging, which is highly beneficial for the detection of tumour cells and tissues. Anticancer therapeutics carried by Mn-LDH more efficiently killed cancer cells than their free counterparts (see figure).

  22. Concepts

    1. Metalloradical Catalysis

      You have full text access to this OnlineOpen article
      Nitrene Radical Intermediates in Catalytic Synthesis

      Dr. Petrus F. Kuijpers, Dr. Ir. Jarl Ivar van der Vlugt, Prof. Sven Schneider and Prof. Dr. Bas de Bruin

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201702537

      Thumbnail image of graphical abstract

      Nitrene radical complexes are reactive intermediates with discrete spin density at the nitrogen atom of the nitrene moiety. They have become important intermediates for organic synthesis. This concept article describes their electronic structure, emphasizes on their usefulness in the catalytic synthesis of various organic products, and highlights the important developments in the field.

  23. Full Papers

    1. Peptides

      One-Pot Self-Assembly of Peptide-Based Cage-Type Nanostructures Using Orthogonal Ligations

      Dr. Eline Bartolami, Jérémie Knoops, Dr. Yannick Bessin, Dr. Mathieu Fossépré, Dr. Joseph Chamieh, Prof. Pascal Dumy, Dr. Mathieu Surin and Dr. Sébastien Ulrich

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201702974

      Thumbnail image of graphical abstract

      All in one pot! The use of orthogonal and chemoselective ligation reactions enables the self-assembly (six components, eight reactions in one-pot) of peptide-based cage nanostructures starting from preorganized cyclic peptides and heterobifunctional spacers.

    2. Anticancer Agents

      Targeted Delivery of a Mannose-Conjugated BODIPY Photosensitizer by Nanomicelles for Photodynamic Breast Cancer Therapy

      Prof. Quan Zhang, Ying Cai, Dr. Qiu-Yan Li, Lin-Na Hao, Zheng Ma, Prof. Xiao-Jun Wang and Prof. Jian Yin

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201702935

      Thumbnail image of graphical abstract

      Therapeutic micelles: Breast cancer cells recognize and internalize nanomicelles co-assembled from a mannose-conjugated BODIPY photosensitizer and Tween 80. These nanomicelles exhibit excellent targeted delivery of the photosensitizer that not only leads to selective cancer cell death but also minimizes damage to normal cells after 665-nm LED light irradiation.

    3. Cooperative Effects

      Excitonically Coupled States in Crystalline Coordination Networks

      Dr. Ritesh Haldar, Antoine Mazel, Reetu Joseph, Michael Adams, Dr. Ian A. Howard, Prof. Dr. Bryce S. Richards, Dr. Manuel Tsotsalas, Dr. Engelbert Redel, Dr. Stéphane Diring, Prof. Dr. Fabrice Odobel and Prof. Dr. Christof Wöll

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201702968

      Thumbnail image of graphical abstract

      Periodically arranged core-substituted naphthalene diimides in a Zn-SURMOF-2 structure exhibit excitonically coupled states.

    4. Inorganic Polymers

      Proof of Concept Studies Directed Towards Designed Molecular Wires: Property-Driven Synthesis of Air and Moisture-Stable Polystannanes

      Jeffrey Pau, Dr. Alan J. Lough, Prof. R. Stephen Wylie, Prof. Robert A. Gossage and Prof. Daniel A. Foucher

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201703453

      Thumbnail image of graphical abstract

      Stan′s the man! Polystannanes with azobenzene ligands demonstrate improved moisture and light stability.

    5. Fluorescence

      Tuning the pKa of Fluorescent Rhodamine pH Probes through Substituent Effects

      Sarah G. Stratton, Grace H. Taumoefolau, Grace E. Purnell, Mona Rasooly, William L. Czaplyski and Prof. Elizabeth J. Harbron

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201703176

      Thumbnail image of graphical abstract

      Deformed dye: The quest for a structure-pKa relationship for fluorescent rhodamine pH probes yields a tale of steric and electronic substituent effects, linear free energy relationships, a crystal structure, and ratiometric fluorescent pH sensing in water with doped conjugated polymer nanoparticles. The pKa values of aniline-derived rhodamine spirolactams can be increased by 2 pH units by employing large substituents to deform the xanthene ring system and electron withdrawing ones to destabilize a key intermediate.

    6. Graphane Complexes

      Anti-Electrostatic CH–Ion Bonding in Decorated Graphanes

      Martin Novák, Prof. Dr. Radek Marek and Dr. Cina Foroutan-Nejad

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201703459

      Thumbnail image of graphical abstract

      Ion–σ interactions: A new class of anti-electrostatic ion–σ bonds between ions and functionalized graphane flakes, G-XYs, is introduced. The strong, long-range electrostatic and Pauli repulsions can be overbalanced by strong orbital interactions (see figure), leading to ion–σ complexes with covalent-type intermolecular bonds as strong as −34 kcal mol−1.

    7. Carbene Complexes | Hot Paper

      Coordination Behavior of a Planar Chiral Cyclic (Amino)(Ferrocenyl)Carbene Ligand in Iridium Complexes

      Yuta Shikata, Risa Yasue and Prof. Kazuhiro Yoshida

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201703467

      Thumbnail image of graphical abstract

      Cafecaesque carbenes: Air- and moisture-stable iridium complexes bearing a new type of chiral carbene ligand, cyclic (amino)(ferrocenyl)carbene (CAFeC), were prepared and fully characterized by NMR spectroscopy and X-ray diffraction analysis. The NMR spectra of the dicarbonyl complex [IrCl(CO)2(CAFeC)] displayed signals for two isomers in solution, which were assigned to diastereomeric rotamers arising from the rotation of the chiral CAFeC ligand around the axes of the Ir−Ccarbene bond. IR spectroscopy of the dicarbonyl complex revealed that the donor strength of CAFeC is much higher than for classic N-heterocyclic carbenes (NHCs) and comparable to cyclic (amino)(alkyl)carbenes (CAACs).

  24. Communications

    1. Rotaxanes

      Rotationally Active Ligands: Dialing-Up Multiple Interlocked Co-Conformations for Silver(I) Coordination

      Dr. Giorgio Baggi and Prof. Dr. Stephen J. Loeb

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201703485

      Thumbnail image of graphical abstract

      Rotaxane roulette: Coordination of AgI ions to the flexible and rotationally active MIM (mechanically interlocked molecule) ligand Ltrans can be likened to playing roulette; the silver ball (AgI ion) tossed at a spinning ([2]rotaxane) wheel will eventually settle into a (binding) pocket, but it may not be the one you bet on!

  25. Cover Pictures

    1. You have free access to this content
      An Efficient Route to Highly Substituted Indoles via Tetrahydroindol-4(5H)-one Intermediates Produced by Ring-Opening Cyclization of Spirocyclopropanes with Amines

      Dr. Hisanori Nambu, Wataru Hirota, Masahiro Fukumoto, Takafumi Tamura and Prof. Dr. Takayuki Yakura

      Version of Record online: 14 SEP 2017 | DOI: 10.1002/chem.201704085

      Thumbnail image of graphical abstract

      An efficient method for the synthesis of highly substituted indoles via tetrahydroindol-4(5H)-one intermediates, prepared by ring-opening cyclization of spirocyclopropanes with amines, was developed. Syntheses of 4-, 5-, 6- or 7-substituted indoles were accomplished by regioselective functionalizations of the intermediates and subsequent oxidation. Furthermore, 4,5,6,7-tetrasubstituted indoles were synthesized by using these regioselective functionalizations. More information can be found in the Full Paper by H. Nambu, T. Yakura et al. (DOI: 10.1002/chem.201702622).

  26. Full Papers

    1. Heterocycles

      The Phosphinoboration of N-Heterocycles

      Dr. Stephen J. Geier, Christopher M. Vogels, Niall R. Mellonie, Erika N. Daley, Dr. Andreas Decken, Dr. Simon Doherty and Prof. Dr. Stephen A. Westcott

      Version of Record online: 13 SEP 2017 | DOI: 10.1002/chem.201702203

      Thumbnail image of graphical abstract

      Do you like Piña colato? The addition of Ph2PBpin (1, pin=pinacolato, O2C2Me4) to a variety of pyridine derivatives and benzofused N-heterocycles results in 1,2- and/or 1,4-addition depending upon the nature of the substrate. Borenium/boronium cation intermediates are implicated in reactions using polar solvents that afford 1,4-addition products.

    2. Enzymes

      Mechanistic Insight into the Binding of Multivalent Pyrrolidines to α-Mannosidases

      Stefania Mirabella, Dr. Giampiero D'Adamio, Dr. Camilla Matassini, Prof. Andrea Goti, Sandra Delgado, Ana Gimeno, Prof. Inmaculada Robina, Dr. Antonio J. Moreno-Vargas, Dr. Sergej Šesták, Prof. Jesús Jiménez-Barbero and Prof. Francesca Cardona

      Version of Record online: 13 SEP 2017 | DOI: 10.1002/chem.201703011

      Thumbnail image of graphical abstract

      Multivalent glycosidase inhibitors: Synthesis, biological evaluation, NMR analysis, and molecular modeling studies underlines, for the first time, the existence of a specific interaction between the jack bean α-mannosidase and pyrrolidine-based multivalent inhibitors. TEM studies suggest the formation of an intermolecular cross-linking network between enzyme and inhibitors.

    3. Dehydrogenation

      Kinetic Studies on Formic Acid Dehydrogenation Catalyzed by an Iridium Complex towards Insights into the Catalytic Mechanism of High-Pressure Hydrogen Gas Production

      Dr. Masayuki Iguchi, Dr. Heng Zhong, Dr. Yuichiro Himeda and Prof. Dr. Hajime Kawanami

      Version of Record online: 13 SEP 2017 | DOI: 10.1002/chem.201702969

      Thumbnail image of graphical abstract

      Rate-limiting step shift: Kinetic studies on the catalytic reaction mechanism of the dehydrogenation of formic acid catalyzed by a water-soluble iridium complex were performed, and a shift of the rate-limiting step at low and high concentrations of formic acid was observed (see figure).

  27. Communications

    1. Nanostructures

      Self-Assembly of Heterogeneously Shaped Nanoparticles into Plasmonic Metamolecules on DNA Origami

      Dr. Wenyan Liu, Dr. Ling Li, Shuo Yang, Prof. Jie Gao and Prof. Risheng Wang

      Version of Record online: 13 SEP 2017 | DOI: 10.1002/chem.201703927

      Thumbnail image of graphical abstract

      Self-assembly of plasmonic metamolecules consisting of heterogeneously shaped metal nanoparticles by using DNA origami as a scaffold is reported. The assembled hetero-PMs exhibit strong interparticle plasmonic coupling in the visible spectra range. This approach provides opportunities to manufacture more complex and advanced materials by integrating diverse nanocomponents with particular properties.

  28. Cover Profile

    1. You have free access to this content
      Stereospecific Winding of Polycyclic Aromatic Hydrocarbons into Trinacria Propellers

      Dario Mosca, Dr. Antoine Stopin, Prof. Dr. Johan Wouters, Dr. Nicola Demitri and Prof. Dr. Davide Bonifazi

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201703996

      Thumbnail image of graphical abstract

      It was through X-ray crystallography that we could unravel the conformation of this molecule, namely the formation of a propeller-like structure.” Read more about the story behind the cover in the Cover Profile and about the research itself on page ▪▪ ff. (DOI: 10.1002/chem.201702032).

  29. Cover Pictures

    1. You have free access to this content
      Crucible-Free Preparation of Transition-Metal Borides: HfB2

      Anne Henschel, Prof. Dr. Michael Binnewies, Dr. Marcus Schmidt, Dr. Horst Borrmann and Prof. Yuri Grin

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201704107

      Thumbnail image of graphical abstract

      The manufacture of metal borides, especially without immixtures of oxygen or nitrogen, is a known problem in the preparation of intermetallic phases. The proof-of-principle for the innovative, crucible-free synthesis of single-phase borides at relatively moderate temperatures by reaction of a metal wire heated by an electrical current with a gaseous boron halide was achieved for hafnium diboride, a material with one of the highest decomposition temperatures. More information can be found in the Communication by Yu. Grin et al. (DOI: 10.1002/chem.201703181).

  30. Communications

    1. Oxidation | Hot Paper

      Transition-Metal-Controlled Inorganic Ligand-Supported Non-Precious Metal Catalysts for the Aerobic Oxidation of Amines to Imines

      Dr. Han Yu, Yongyan Zhai, Guoyong Dai, Shi Ru, Prof. Sheng Han and Prof. Yongge Wei

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201703185

      Thumbnail image of graphical abstract

      A breath of fresh air: A mild aerobic oxidative coupling protocol of primary and secondary amines as well as the coupling of alcohols and amines to afford corresponding imines was developed with inorganic ligand-supported metal catalyst (NH4)n[MMo6O18(OH)6] (M=Cu2+, Fe3+, Co3+, Ni2+, Zn2+). This method utilizes mainly an inorganic polymolybdate ligand to support the Cu2+ ion and 1 atm O2 gas as the sole oxidant, which can smoothly proceed to afford various imines in high yields and selectivity, avoiding the use of expensive, toxic, air/moisture sensitive, and commercially unavailable organic ligands.

  31. Full Papers

    1. Energy Storage

      Potassium (De-)insertion Processes in Prussian Blue Particles: Ensemble versus Single Nanoparticle Behaviour

      Dr. Giorgia Zampardi, Stanislav V. Sokolov, Dr. Christopher Batchelor-McAuley and Prof. Dr. Richard G. Compton

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201703175

      Thumbnail image of graphical abstract

      PB&J: Potassium insertion and deinsertion processes were investigated in Prussian blue at the nanoscale through the nanoimpact method. The electrochemical behaviour of the material at the single particle was confronted to the one at the composite level, which is influenced by the presence of conductive additives and polymeric binder.

    2. Host–Guest Systems | Very Important Paper

      You have free access to this content
      Understanding Carbon Dioxide Solubility in Ionic Liquids by Exploring the Link with Liquid Clathrate Formation

      Dr. Steven P. Kelley, Luis A. Flores, Matthew S. Shannon, Prof. Jason E. Bara and Prof. Robin D. Rogers

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201703117

      Thumbnail image of graphical abstract

      Benzene and CO2 dissolution in ionic liquids for CO2 capture are related phenomena, and increases in benzene solubility parallel increases in CO2 solubility.

  32. Communications

    1. Medicinal Chemistry

      Design, Synthesis, and Characterization of Brequinar Conjugates as Probes to Study DHODH Inhibition

      Joseph T. Madak, Christine R. Cuthbertson, Dr. Wenmin Chen, Prof. Dr. Hollis D. Showalter and Prof. Dr. Nouri Neamati

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201702999

      Thumbnail image of graphical abstract

      Brequin′ news: A novel convergent synthesis of brequinar-based probes to induce protein degradation (16 steps) and improve mitochondria accumulation (four steps) is disclosed.

  33. Cover Profile

    1. You have free access to this content
      Determination of the Absolute Configuration of (−)-Hydroxynitrilaphos and Related Biosynthetic Questions

      Dr. Katharina Pallitsch, Barbara Happl and Christian Stieger

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201703497

      Thumbnail image of graphical abstract

      We decided to present phosphonate biochemistry as what it still is: a kind of magic.” Read more about the story behind the cover in the Cover Profile and about the research itself on page ▪▪ ff. (DOI: 10.1002/chem.201702904).

  34. Communications

    1. Asymmetric Synthesis

      Organocatalytic Asymmetric Synthesis of trans-γ-Lactams

      Dr. Shunxi Dong, Marcus Frings, Duo Zhang, Qianqian Guo, Dr. Constantin G. Daniliuc, Hanchao Cheng and Prof. Dr. Carsten Bolm

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201703263

      Thumbnail image of graphical abstract

      An N-heterocyclic carbene (NHC)-catalyzed highly diastereo- and enantioselective formal [3+2] reaction of o-hydroxy aromatic aldimines and cinnamaldehydes leading to enantioenriched trans-γ-lactams was developed. Subsequent transformations allowed modifying the heterocyclic core of the products. An organocatalytic kinetic resolution of chiral lactams was demonstrated in a first proof-of-principle study.

    2. Radical Reactions

      Catalyzed Radical Termination in the Presence of Tellanyl Radicals

      Thomas G. Ribelli, Dr. S. M. Wahidur Rahaman, Prof. Krzysztof Matyjaszewski and Prof. Rinaldo Poli

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201703064

      Thumbnail image of graphical abstract

      The bimolecular termination of (CH3)2C.CO2CH3 radicals generated from V-601 is essentially solvent- and temperature independent, contrary to that of the same radicals generated from (CH3)2C(TeMe)CO2CH3; DFT calculations and V-601 photolysis in the presence of Te2Ph2 suggest an unprecedented Te-catalyzed disproportionation to account for these different results (see figure).

  35. Full Papers

    1. Heterocycles

      Non-Planar [n]Cyclo-1,8-carbazolylenes (n=3,4,6) and [3]Cyclo-1,8-carbazolylenyl B, P, PO, SiPh Complexes

      Dr. Koji Yamamoto, Dr. Palash Pandit and Prof. Dr. Shuhei Higashibayashi

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201702853

      Thumbnail image of graphical abstract

      A bowl-shaped cyclodimer, a flake-shaped cyclotrimer, a double-decker-ring-shaped cyclotetramer and a cyclohexamer of carbazole were synthesized by Ni0-mediated one-shot cyclo-oligomerization of 1,8-dibromocarbazole, and were named [n]cyclo-1,8-carbazolylenes (n=3,4,6; see scheme). [3]Cyclo-1,8-carbazolylene acted as a trivalent tridentate ligand for B, P, Si atoms, giving distorted flake-shaped [3]cyclo-1,8-carbazolylenyl complexes.

    2. Molecular Dynamics

      A New Pathway for Protein Haptenation by β-Lactams

      Dr. Raúl Pérez-Ruíz, Dr. Emilio Lence, Dr. Inmaculada Andreu, Dr. Daniel Limones-Herrero, Prof. Concepción González-Bello, Prof. Miguel A. Miranda and Prof. M. Consuelo Jiménez

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201702643

      Thumbnail image of graphical abstract

      Cause of photoallergy: A new haptenation mechanism of β-lactams drugs, which constitute the key step in the sequence of events leading to photoallergy, has been identified. Selecting human serum albumin as a target protein and ezetimibe as a probe, the covalent modification of Lys414 and Lys525 residues (located in sub-domains IIIA and IIIB) has been identified (see figure).

    3. Surface Analysis

      Functionalized Acupuncture Needle as Surface-Enhanced Resonance Raman Spectroscopy Sensor for Rapid and Sensitive Detection of Dopamine in Serum and Cerebrospinal Fluid

      Pan Li, Binbin Zhou, Xiaomin Cao, Xianghu Tang, Prof. Dr. Liangbao Yang, Prof. Dr. Ling Hu and Prof. Dr. Jinhuai Liu

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201702607

      Thumbnail image of graphical abstract

      Beyond the tip: Acupuncture needles decorated with gold nanoparticles functionalized with ferric citrate (Au NPs/CA-FeIII) act as a surface-enhanced resonance Raman spectroscopy (SERRS) sensor for the sensitive and selective detection of dopamine (DA) with a fast signal response and simple operation for use in complicated specimens (see figure).

  36. Concepts

    1. Molecular Devices

      Spatial and Lateral Control of Functionality by Rigid Molecular Platforms

      Michal Valášek and Marcel Mayor

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201703349

      Thumbnail image of graphical abstract

      The concept of rigid molecular platforms, such as molecular tripods or flat multipodal molecules, is a promising strategy to immobilize active functionality of tailor-made molecules atop flat surfaces, particularly in view of potential exploitation for the fabrication of functional devices. The main focus is set on the different molecular designs to control the spatial arrangement of functional 3D molecular architectures on surfaces and to form mechanically stable contact to the underlying substrate.

  37. Full Papers

    1. Supramolecular Cages

      You have full text access to this OnlineOpen article
      Homochiral Emissive Λ8- and Δ8-[Ir8Pd4]16+ Supramolecular Cages

      Diego Rota Martir, Dr. Daniel Escudero, Prof. Denis Jacquemin, Dr. David B. Cordes, Prof. Alexandra M. Z. Slawin, Dr. Herbert A. Fruchtl, Dr. Stuart L. Warriner and Dr. Eli Zysman-Colman

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201703273

      Thumbnail image of graphical abstract

      Caged in: Emissive and homochiral supramolecular Pd4L8 cages have been prepared by self-assembly between Pd2+ ions and two families of enantiopure metalloligands, Λ- and Δ-[Ir(mesppy)2(qpy)]BF4 and Λ- and Δ-[Ir(dFmesppy)2(qpy)]BF4 (mesppy=2-phenyl-4-mesitylpyridinato and dFmesppy=2-(4,6-difluorophenyl)-4-mesitylpyridinato, and qpy is 4,4′:2′,2′′:4′′,4′′′-quaterpyridine). These polycationic cages selectively encapsulate anionic compounds. These cages are promising candidates as chiral photoactive containers capable of absorbing photons and transferring light energy to or from encapsulated guest acceptors.

    2. Peptide-Polymer Conjugates

      Structural Characterization of PEGylated Hexaphenylalanine Nanostructures Exhibiting Green Photoluminescence Emission

      Dr. Carlo Diaferia, Dr. Teresa Sibillano, Dr. Davide Altamura, Dr. Valentina Roviello, Dr. Luigi Vitagliano, Dr. Cinzia Giannini, Prof. Giancarlo Morelli and Dr. Antonella Accardo

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201703055

      Thumbnail image of graphical abstract

      Aggregating peptides: Changes in the length and composition of the PEG chain have been found to modulate the structural organization of PEGylated poly(phenylalanine)-based nanostructures and their optoelectronic properties. More extended electron delocalization through hydrogen bonds and different degrees of order/disorder in the fibrillary nanostructure cause a redshift of the intrinsic photoluminescence of the fiber (see figure).

  38. Cover Pictures

    1. You have free access to this content
      Increased Conformational Flexibility of a Macrocycle–Receptor Complex Contributes to Reduced Dissociation Rates

      Dr. Adrian Glas, Eike-Christian Wamhoff, Dr. Dennis M. Krüger, Dr. Christoph Rademacher and Prof. Dr. Tom N. Grossmann

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201704109

      Thumbnail image of graphical abstract

      State-of-the-art isothermal titration calorimetry, 19F NMR spectroscopy and molecular dynamics simulations reveal unexpected differences in the binding kinetics of closely related macrocycles. Most strikingly, increased flexibility of the bound macrocycle correlates with elongated receptor residence time. These findings highlight the potential of loop-like peptide epitopes as starting point for macrocyclic peptidomimetics. More information can be found in the Communication by C. Rademacher, T. N. Grossmann et al. (DOI: 10.1002/chem.201702776).

    2. You have free access to this content
      Laying Waste to Mercury: Inexpensive Sorbents Made from Sulfur and Recycled Cooking Oils

      Max J. H. Worthington, Renata L. Kucera, Inês S. Albuquerque, Dr. Christopher T. Gibson, Alexander Sibley, Dr. Ashley D. Slattery, Dr. Jonathan A. Campbell, Salah F. K. Alboaiji, Katherine A. Muller, Jason Young, Nick Adamson, Dr. Jason R. Gascooke, Dr. Deshetti Jampaiah, Dr. Ylias M. Sabri, Prof. Suresh K. Bhargava, Dr. Samuel J. Ippolito, Prof. David A. Lewis, Prof. Jamie S. Quinton, Prof. Amanda V. Ellis, Dr. Alexander Johs, Dr. Gonçalo J. L. Bernardes and Dr. Justin M. Chalker

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201704108

      Thumbnail image of graphical abstract

      With the Minamata Convention coming into force this year, there is a growing requirement for low-cost sorbents for mercury pollution. Thus, a polysulfide was prepared by the co-polymerization of sulfur and canola oil. As sulfur is a byproduct of the petroleum industry and used cooking oils are suitable starting materials, the resulting sorbent can be prepared entirely from waste. This high-sulfur rubber was effective in trapping diverse forms of mercury including mercury metal, inorganic mercury, and organomercury compounds. More information can be found in the Full Paper by J. M. Chalker et al. (DOI: 10.1002/chem.201702871).

  39. Communications

    1. Phosphorescence

      The Chameleonic Nature of Platinum(II) Imidazopyridine Complexes

      Piermaria Pinter, Rebecca Pittkowski, Johannes Soellner and Prof. Dr. Thomas Strassner

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201703908

      Thumbnail image of graphical abstract

      Imidazopyridine C^C* platinum(II) complexes show unique photophysical properties: aggregation induced enhancement of the quantum yields with simultaneous decrease of phosphorescence lifetimes. Additionally, a change of emission color is induced by variation of the excitation wavelength. The aggregation behavior is controlled by the steric demand of the substituents. The complexes are excellent room temperature phosphorescent blue emitters with emission maxima below 470 nm and quantum yields of up to 93 %.

    2. Rearrangements

      Revealing the Activity of π-Acid Catalysts using a 7-Alkynyl Cycloheptatriene

      Marie Vayer, Dr. Regis Guillot, Dr. Christophe Bour and Prof. Vincent Gandon

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201703817

      Thumbnail image of graphical abstract

      Choose your own adventure: A simple benchmark reaction allows prediction of the transformations that can be catalyzed by a new complex. Soft π acids follow a carbenoid pathway leading to indenes from a 7-alkynyl cycloheptatriene. Harder π acids follow a “large proton” pathway, yielding a hydroarylation product. If these hard species liberate protons in the reaction mixture, the latter further cyclizes into a tricyclic product.

  40. Full Papers

    1. Doped Carbon Networks

      N/S Co-Doped 3 D Porous Carbon Nanosheet Networks Enhancing Anode Performance of Sodium-Ion Batteries

      Lei Zou, Prof. Yanqing Lai, Hongxing Hu, Mengran Wang, Dr. Kai Zhang, Peng Zhang, Dr. Jing Fang and Prof. Jie Li

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201702182

      Thumbnail image of graphical abstract

      Advantageous anodes: The N/S co-doped 3 D porous carbon nanosheet network delivers excellent long-term cycling performance, with a capacity of up to 214.9 mA h g−1 after 2000 charge/discharge cycles at 0.5 A g−1. Its superior performance is attributed to its high number of mesopores, large surface area, and large number of edge defects resulting from the N/S co-doping. This material is a promising alternative for large-scale stationary energy applications.

  41. Communications

    1. Cycloaddition

      Diversity-Oriented Syntheses by Combining CuAAC and Stereoselective INCIC Reactions with Peptides

      Yuanyuan Wang, Prof. Anders Ø. Madsen, Prof. Frederik Diness and Prof. Morten Meldal

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201702900

      Thumbnail image of graphical abstract

      Two new cascade reactions of N-carbamoyl iminium ions, including a stereoselective double cyclization generating N,N′-aminals and an acid-promoted auto-oxidation, are described. Both new reactions proved to be completely orthogonal to a subsequent CuAAC reaction. The application to diversity-oriented synthesis was demonstrated in solution and on solid support.

    2. Energetic Materials

      Manganese-Mediated Linkage of Perchlorate to Aminotetrazoles Produces Twice the Energy Density of the Unmetalated Salt

      Owen T. O'Sullivan and Prof. Michael J. Zdilla

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201702696

      Thumbnail image of graphical abstract

      Energy to burn: Energy density of a tetrazole-based, perchlorate-containing energetic material is increased by covalent attachment of the strongly oxidizing perchlorate anions into the structure.

  42. Full Papers

    1. Cancer-Cell Imaging

      Unveiling NIR Aza-Boron-Dipyrromethene (BODIPY) Dyes as Raman Probes: Surface-Enhanced Raman Scattering (SERS)-Guided Selective Detection and Imaging of Human Cancer Cells

      Dr. Nagappanpillai Adarsh, Adukkadan N. Ramya, Dr. Kaustabh Kumar Maiti and Dr. Danaboyina Ramaiah

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201702626

      Thumbnail image of graphical abstract

      Raman mapping: The unique Raman activity of aza-BODIPY dyes at the molecular level, as well as their SERS upon adsorption onto nano-roughened gold surface, is described. The nanoprobe successfully targets HT1080 cell lines, thus facilitating effective detection and Raman mapping (see figure).

    2. Chemical Biology

      Effects of Fluorophore Attachment on Protein Conformation and Dynamics Studied by spFRET and NMR Spectroscopy

      Dr. Carolina Sánchez-Rico, Dr. Lena Voith von Voithenberg, Dr. Lisa Warner, Prof. Don C. Lamb and Prof. Michael Sattler

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201702423

      Thumbnail image of graphical abstract

      Fluorophore effect on proteins: Using spFRET and NMR spectroscopy, the effect of various fluorophores on the conformation and dynamics of the splicing factor U2AF65 were studied. The site of attachment and type of fluorophore can significantly affect the conformation of the protein through transient interactions with the protein surface. The fluorophore should be chosen according to its photophysical properties and by avoiding hydrophobicity of the dye.

    3. Hybrid Materials

      Thermosensitive Cation-Selective Mesochannels: PNIPAM-Capped Mesoporous Thin Films as Bioinspired Interfacial Architectures with Concerted Functions

      Sonja Schmidt, Sebastián Alberti, Prof. Philipp Vana, Prof. Galo J. A. A. Soler-Illia and Prof. Omar Azzaroni

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201702368

      Thumbnail image of graphical abstract

      Nanoarchitectonic shift: This work reports the use of PNIPAM-capped mesoporous silica thin films as thermosensitive cation-selective mesochannels. The “nanoarchitectonic” approach presented here could provide new routes toward the generation of heterosupramolecular nanosystems displaying addressable transport properties similar to those encountered in biological ion channels.

  43. Minireviews

    1. Organic Frameworks

      Redox Active Metal– and Covalent Organic Frameworks for Energy Storage: Balancing Porosity and Electrical Conductivity

      Dr. Yugen Zhang, Dr. Siti Nurhanna Riduan and Dr. Jinquan Wang

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201702919

      Thumbnail image of graphical abstract

      Finding a balance: Redox-active metal–organic frameworks (MOF) and covalent organic frameworks (COF) have been recently developed as electrode materials for energy storage devices. An equilibrium between stability, porosity and electrical conductivity must be achieved before they can be applied as electrode materials in energy storage devices.

  44. Full Papers

    1. Lithium Complexes

      Experimental and Computational Studies of the Structure of Sulfonimidoyl Vinyllithiums

      Dr. Alexander Walter Giesen, Prof. Dr. Gerhard Raabe, Dr. Jan Runsink and Prof. Dr. Hans-Joachim Gais

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201701881

      Thumbnail image of graphical abstract

      Sulfonimidoyl vinyllithiums are monomeric CIPs with a C−Li bond, which contain six- or four-membered chelate rings, depending on the substituent at the N atom. (N-Sulfonyl)sulfonimidoyl methyllithium adopts a similar six-membered chelate ring structure.

    2. Bioinorganic Chemistry

      Control of Reversible Activation Dynamics of [Ru{η61-C6H5(C6H4)NH2}(XY)]n+ and the Effect of Chelating-Ligand Variation

      Francisco Martínez-Peña and Dr. Ana M. Pizarro

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201701681

      Thumbnail image of graphical abstract

      End of the tether: A new family of activatable ruthenium tethered arene complexes was synthesized and characterized. These metal complexes can reversibly open and close a vacant position for interaction with biomolecules. Both the activation and inactivation processes are pH-dependent. This class of RuII tether complexes represent a first step towards rational design of pH-responsive organometallic switches with promising applications in cancer research.

    3. Antisense Agents

      Towards Improved Oligonucleotide Therapeutics Through Faster Target Binding Kinetics

      Dr. Mirjam Menzi, Dr. Bettina Wild, Dr. Ugo Pradère, Anna L. Malinowska, Dr. Andreas Brunschweiger, Dr. Helen L. Lightfoot and Prof. Dr. Jonathan Hall

      Version of Record online: 12 SEP 2017 | DOI: 10.1002/chem.201701670

      Thumbnail image of graphical abstract

      Nature-inspired modification of RNA for faster hybridization: The conjugation of spermine groups using a triazole linker to 2′-O-methyloligoribonucleo tides leads to accelerated binding to complementary RNAs. The conjugated fragments in the major groove mimic the actions of natural polyamines with cellular RNAs and greatly increase hybridization affinities.

    4. Chalcogenides

      Flower-like MoSe2/C Composite with Expanded (0 0 2) Planes of Few-layer MoSe2 as the Anode for High-Performance Sodium-Ion Batteries

      Prof. Jie Li, Hongxing Hu, Furong Qin, Peng Zhang, Lei Zou, Haobo Wang, Dr. Kai Zhang and Prof. Yanqing Lai

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201702791

      Thumbnail image of graphical abstract

      Layered anodes: A simple one-pot hydrothermal synthesis followed by heat treatment forms composite flower-like anode materials of MoSe2 and carbon. Expansion of the interlayer spacing enhances the intercalation kinetics and leads to improved cycling performance of the battery system.

  45. Communications

    1. Titanates | Hot Paper

      You have free access to this content
      Benign Synthesis of Black Microspheres of Anatase TiO2 with Paramagnetic Oxygen Vacancies through NH3 Treatment

      Dr. Qysar Maqbool and Dr. Aasheesh Srivastava

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201702343

      Thumbnail image of graphical abstract

      Black ball: A facile, two-step synthesis of phase-pure black anatase microspheres (B-TiO2) with paramagnetic oxygen vacancies is reported.

    2. Fluorescence Labeling

      Simple Light-Triggered Fluorescent Labeling of Silica Nanoparticles for Cellular Imaging Applications

      Rui Sun, Dr. Ling Yin, Dr. Shaohua Zhang, Lei He, Xiaju Cheng, Anna Wang, Huawei Xia and Prof. Haibin Shi

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201703653

      Thumbnail image of graphical abstract

      Keeping it simple: A simple light-triggered fluorescent labeling approach has been developed, which enables facile and mild fluorescently labeling of silica nanoparticles for cellular imaging applications.

  46. Full Papers

    1. Natural Products | Hot Paper

      You have full text access to this OnlineOpen article
      Total Synthesis of the Schisandraceae Nortriterpenoid Rubriflordilactone A

      Dr. Guilhem Chaubet, Shermin S. Goh, Mujahid Mohammad, Dr. Birgit Gockel, Marie-Caroline A. Cordonnier, Hannah Baars, Andrew W. Phillips and Prof. Edward A. Anderson

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201703229

      Thumbnail image of graphical abstract

      Total terpenoids: The total synthesis of the Schisandraceae nortriterpene rubriflordilactone A is reported. Palladium- and cobalt-catalyzed polycyclizations were employed as key strategies to construct the central arene D ring from bromoendiyne and triyne precursors. A number of model systems were explored to investigate these two methodologies, and also to establish routes for the installation of the challenging benzopyran and butenolide rings.

    2. Cancer Therapy | Hot Paper

      Porphyrins Conjugated with Peripheral Thiolato Gold(I) Complexes for Enhanced Photodynamic Therapy

      Jean-François Longevial, Dr. Khaled El Cheikh, Dr. Dina Aggad, Aurélien Lebrun, Dr. Arie van der Lee, Dr. Frederik Tielens, Dr. Sébastien Clément, Prof. Alain Morère, Dr. Marcel Garcia, Dr. Magali Gary-Bobo and Dr. Sébastien Richeter

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201702975

      Thumbnail image of graphical abstract

      Porphyrins fused to N-heterocyclic carbene gold(I) complexes were synthesized and used as photosensitizers for photodynamic therapy on MCF-7 cancer cells. Data show that the observed photodynamic effect depends on the nature of the ancillary thiolato ligands linked to gold(I).

    3. Mo2 Complexes

      C−C and C−N Couplings Following Hydride Addition on Isocyanide Cyclopolyenyl Dimolybdenum Complexes to Give Tethered Aldimine and Aminocarbene Derivatives

      Dr. Belén Alvarez, Dr. M. Angeles Alvarez, Prof. Dr. M. Esther García, Dr. Daniel García-Vivó and Prof. Dr. Miguel A. Ruiz

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201702998

      Thumbnail image of graphical abstract

      All starts at the Cp ligand! Hydride attack on the cations [Mo2Cp2{μ-κ2P,E1P5-EP(C6H3tBu3)}(CNR)(CO)2]+ (E=S, Se) is initiated at the Cp ligand, but eventually reaches the CNR ligand, this being followed by competitive C−C and C−N couplings to the C6 ring, to yield aldimine and aminocarbene derivatives, respectively (see graphic), the latter being the kinetic products of these reactions (Mo*=MoCp(CO)2; •=C-tBu).

  47. Communications

    1. Macromolecules

      Combining Two Methods of Sequence Definition in a Convergent Approach: Scalable Synthesis of Highly Defined and Multifunctionalized Macromolecules

      Susanne C. Solleder, Steven Martens, Pieter Espeel, Prof. Dr. Filip Du Prez and Prof. Dr. Michael A. R. Meier

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201703877

      Thumbnail image of graphical abstract

      Little by little: The first combination of efficient thiolactone chemistry and the Passerini three-component reaction (P-3CR) for the synthesis of sequence-defined macromolecules is reported. The thiolactone moiety was used as protecting group for the thiol, allowing the synthesis of a library of sequence-defined α,ω-functionalized building blocks. These building blocks were subsequently coupled to oligomers to give larger oligomers with molecular weights of up to 4629.73 g mol−1 in gram quantities with up to 15 independently selectable side chains.

  48. Cover Pictures

    1. You have free access to this content
      Solvent-Induced Cadmium(II) Metal–Organic Frameworks with Adjustable Guest-Evacuated Porosity: Application in the Controllable Assembly of MOF-Derived Porous Carbon Materials for Supercapacitors

      Man-Li Yue, Yi-Fan Jiang, Lin Zhang, Cheng-Yan Yu, Kang-Yu Zou and Prof. Zuo-Xi Li

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201704084

      Thumbnail image of graphical abstract

      Five Cd-MOFs, constructed from identical ligand ingredients under different solvents, were employed as precursors to prepare porous carbons (PCs) through a calcination process. The results reveal that the specific surface area of PCs is closely related to the porosity of Cd-MOFs, and both could be adjusted by the solvent. PCs were further activated by KOH to obtain APCs, and the APC-dmf electrode exhibits the highest porosity, largest specific capacitance, and excellent cycling stability, which has a potential application in supercapacitors. More information can be found in the Full Paper by Z.-X. Li et al. (DOI: 10.1002/chem.201702694).

    2. You have free access to this content
      Creation of Optically Pure Crystals from a Meso-Type Gold(I) Metalloligand with d- and l-Amino Acids: A Coordination Trick

      Dr. Takuma Itai, Dr. Tatsuhiro Kojima, Dr. Naoto Kuwamura and Prof. Dr. Takumi Konno

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201704086

      Thumbnail image of graphical abstract

      Optically pure crystals from a meso-compound with d- and l-amino acids have been created for the first time. The reactions of a meso-digold(I) complex containing both d- and l-penicillamine with MII (NiII, ZnII) yielded neutral AuI2MII complexes, which are chiral (C vs. A) at the metal centers. By spontaneous resolution, AuI2MII complexes gave optically pure C- and A-crystals, showing the creation of homochirality from meso-digold(I) complex and achiral M2+ through crystallization; that is the “Coordination Trick” in this case. Such a phenomenon has not been observed for cationic AuI2CoIII complex, giving a racemic compound containing both C- and A-isomers. More information can be found in the Communication by T. Konno et al. (DOI: 10.1002/chem.201703350).

    3. You have free access to this content
      Investigating Intracellular Localisation and Cytotoxicity Trends for Neutral and Cationic Iridium Tetrazolato Complexes in Live Cells

      Chiara Caporale, Dr. Christie A. Bader, Dr. Alexandra Sorvina, Karen D. M. MaGee, Prof. Brian W. Skelton, Todd A. Gillam, Dr. Phillip J. Wright, Prof. Paolo Raiteri, Prof. Stefano Stagni, Prof. Janna L. Morrison, Dr. Sally E. Plush, Prof. Douglas A. Brooks and Prof. Massimiliano Massi

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201704087

      Thumbnail image of graphical abstract

      Luminescent iridium tetrazolato complexes can be exploited for live cell imaging, and their cellular localization can be modulated by simple methylation of these neutral species to yield the corresponding cationic complexes. The neutral family of complexes displays a tendency to accumulate within the endoplasmic reticulum and, to a variable extent, lipid droplets. The analogous cationic complexes display a tendency to localize primarily in mitochondria. Interestingly, the neutral complexes highlight very low cytotoxicity when compared to their corresponding cationic species. More information can be found in the Full Paper S. E. Plush, D. A. Brooks, M. Massi et al. (DOI: 10.1002/chem.201701352).

  49. Full Papers

    1. Macrocycles

      Supramolecular Host–Guest Inclusion for Distinguishing Cucurbit[7]uril-Based Pseudorotaxanes from Small-Molecule Ligands in Coordination Assembly with a Uranyl Center

      Dr. Lei Mei, Zhen-Ni Xie, Dr. Kong-qiu Hu, Dr. Li-Yong Yuan, Dr. Zeng-Qiang Gao, Prof. Zhi-Fang Chai and Prof. Wei-Qun Shi

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201702752

      Thumbnail image of graphical abstract

      Beyond small-molecule-based coordination assembly: Bulky cucurbit[7]uril macrocycle exerts significant influence on the groups of the guest ligand threading in it, and achieves structural diversity of as-generated uranyl compounds by combined effects of improved stability and increased steric hindrance for the cucurbit[7]uril-encapsulated pseudorotaxane linker.

    2. Density Functional Calculations

      The Unusual Role of Aromatic Solvent in Single-Site AluminumI Chemistry: Insights from Theory

      Shailja Jain and Dr. Kumar Vanka

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201701642

      Thumbnail image of graphical abstract

      More than a spectator: Computational investigations with DFT show that the efficiency of H−H, H−N, and H−P σ-bond activation by the NacNac AlI complex in the presence of explicit benzene solvent molecules is several orders of magnitude higher than that in its absence (see figure). This indicates metal–solvent cooperativity in main-group chemistry.

    3. Sensors

      Solvent-Free Off–On Detection of the Improvised Explosive Triacetone Triperoxide (TATP) with Fluorogenic Materials

      Patricia Calvo-Gredilla, José García-Calvo, Dr. José V. Cuevas, Prof. Tomás Torroba, Dr. Jesús-Luis Pablos, Dr. Félix C. García, Prof. José-Miguel García, Nathalie Zink-Lorre, Dr. Enrique Font-Sanchis, Prof. Ángela Sastre-Santos and Prof. Fernando Fernández-Lázaro

      Version of Record online: 8 SEP 2017 | DOI: 10.1002/chem.201702412

      Thumbnail image of graphical abstract

      Spontaneous glow: A fluorogenic perylenediimide-functionalized polyacrylate is capable of generating color and fluorescence changes in the presence of triacetone triperoxide (TATP), which is an improvised explosive used in terrorist attacks, under solvent-free, solid-state conditions (see figure).

SEARCH

SEARCH BY CITATION