Angewandte Chemie International Edition

Cover image for Vol. 54 Issue 23

Editor: Peter Gölitz, Deputy Editors: Neville Compton, Haymo Ross

Online ISSN: 1521-3773

Associated Title(s): Angewandte Chemie, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemPlusChem, Zeitschrift für Chemie

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The following papers are very important in the opinion of two referees.

You are invited to comment on published VIPs. Please use the link given at the end of each such abstract. Scientific comments may be forwarded to the authors by the editorial office and may be posted on this page. Kindly let us know if your comments are for the editorial office only, the author, or the public as well.

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Merging Photoredox and Nickel Catalysis: The Direct Synthesis of Ketones by the Decarboxylative Arylation of α-Oxo Acids

Dr. Lingling Chu, Jeffrey M. Lipshultz and Prof. Dr. David W. C. MacMillan

Merging Photoredox and Nickel Catalysis: The Direct Synthesis of Ketones by the Decarboxylative Arylation of α-Oxo AcidsThe direct decarboxylative arylation of α-oxo acids has been achieved by synergistic visible-light-mediated photoredox and nickel catalysis. This method offers rapid entry to aryl and alkyl ketone architectures from simple α-oxo acid precursors via an acyl radical intermediate. Significant substrate scope is observed with respect to both the oxo acid and arene coupling partners.

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Pseudohalide-Induced Moisture Tolerance in Perovskite CH3NH3Pb(SCN)2I Thin Films

Qinglong Jiang, Dominic Rebollar, Jue Gong, Elettra L. Piacentino, Prof. Chong Zheng and Prof. Tao Xu

Pseudohalide-Induced Moisture Tolerance in Perovskite CH3NH3Pb(SCN)2I Thin FilmsThe replacement of two iodides by two pseudohalide thiocyanate ions in CH3NH3PbI3 results in a perovskite material with superior tolerance to moisture when used as the active material of a solar cell. For the CH3NH3Pb(SCN)2I perovskite films, no significant degradation was observed after the film had been exposed to air with a relative humidity of 95 % for over four hours, whereas the CH3NH3PbI3 films degraded in less than 1.5 hours.

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Photoinduced Charge-Carrier Generation in Epitaxial MOF Thin Films: High Efficiency as a Result of an Indirect Electronic Band Gap?

Dr. Jinxuan Liu, Wencai Zhou, Jianxi Liu, Dr. Ian Howard, Dr. Goran Kilibarda, Dr. Sabine Schlabach, Damien Coupry, Dr. Matthew Addicoat, Satoru Yoneda, Yusuke Tsutsui, Dr. Tsuneaki Sakurai, Prof. Dr. Shu Seki, Dr. Zhengbang Wang, Peter Lindemann, Dr. Engelbert Redel, Prof. Thomas Heine and Prof. Dr. Christof Wöll

Photoinduced Charge-Carrier Generation in Epitaxial MOF Thin Films: High Efficiency as a Result of an Indirect Electronic Band Gap?Mind the gap: electronic-structure calculations show that ordered arrays of porphyrins have a small dispersion of occupied and unoccupied bands leading to the formation of a small indirect band gap. Such ordered structures are formed by liquid-phase epitaxy (see picture) and exhibit superior photophysical properties. A prototype organic photovoltaic device based on this material is highly efficient.

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Orthogonal Light-Induced Self-Assembly of Nanoparticles using Differently Substituted Azobenzenes

Dr. Debasish Manna, Dr. Thumu Udayabhaskararao, Dr. Hui Zhao and Dr. Rafal Klajn

Orthogonal Light-Induced Self-Assembly of Nanoparticles using Differently Substituted AzobenzenesA guiding light: Nanoparticles functionalized with variously substituted azobenzenes self-assemble into aggregates in response to different wavelengths of light. Exposing a mixture of differently sized nanoparticles, each functionalized with a different azobenzene, to light of a specific color (ultraviolet or blue) induces the selective self-assembly of only one type of the nanoparticles. Irradiation with the other wavelength triggers the disassembly of the aggregates, and the simultaneous self-assembly of nanoparticles of the other type.

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Textile/Metal–Organic-Framework Composites as Self-Detoxifying Filters for Chemical-Warfare Agents

Elena López-Maya, Dr. Carmen Montoro, Dr. L. Marleny Rodríguez-Albelo, Dr. Salvador D. Aznar Cervantes, Dr. A. Abel Lozano-Pérez, Prof. José Luis Cenís, Dr. Elisa Barea and Prof. Jorge A. R. Navarro

Textile/Metal–Organic-Framework Composites as Self-Detoxifying Filters for Chemical-Warfare AgentsThe silk of human kindness: Insertion of lithium alkoxides in zirconium metal–organic frameworks (MOF) which are then deposited on silk fibers gives rise to protective fabrics capable of self-detoxifying chemical-warfare agents. The fabrics combine the air-permeation properties of the textiles with the highly active phosphotriesterase catalytic activity of the MOF for the hydrolysis of P[BOND]F, P[BOND]O, and C[BOND]Cl bonds.

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A Molecular Nanotube with Three-Dimensional π-Conjugation

Dr. Patrik Neuhaus, Dr. Arjen Cnossen, Juliane Q. Gong, Prof. Laura M. Herz and Prof. Harry L. Anderson

A Molecular Nanotube with Three-Dimensional π-ConjugationJoining together six staves creates a barrel-shaped nanotube consisting of twelve porphyrin units with continuous cylindrical π-conjugation. Fluorescence measurements reveal ultrafast migration of electronic excitation between different regions of the nanotube.

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Ring Tension Applied to Thiol-Mediated Cellular Uptake

Dr. Giulio Gasparini, Dr. Gevorg Sargsyan, Dr. Eun-Kyoung Bang, Dr. Naomi Sakai and Prof. Stefan Matile

Ring Tension Applied to Thiol-Mediated Cellular UptakeMounting tension: Ring tension, which has been exploited for the modification of biological systems in many different ways, with click chemistry being a notable example, was applied to thiol-mediated cellular uptake. Fluorescent probes were conjugated to cyclic disulfides with varying degrees of ring tension and uptake into human cells was found to increase with increasing tension.

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How the [NiFe4S4] Cluster of CO Dehydrogenase Activates CO2 and NCO

Jochen Fesseler, Dr. Jae-Hun Jeoung and Prof. Dr. Holger Dobbek

How the [NiFe4S4] Cluster of CO Dehydrogenase Activates CO2 and NCO−Two sides of the same coin: CO2 and NCO are both activated at Ni and Fe2 of the [NiFe4S4] cluster of CO dehydrogenase and bind as bridging ligands between the two metal atoms. Insights from true atomic resolution structures draw a clear picture of the chemical nature of the ligands: activation of both the substrate CO2 and the inhibitor NCO occurs by formal two-electron reduction.

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Oxygen Reduction Mediated by Single Nanodroplets Containing Attomoles of Vitamin B12: Electrocatalytic Nano-Impacts Method

Dr. Wei Cheng and Prof. Dr. Richard G. Compton

Oxygen Reduction Mediated by Single Nanodroplets Containing Attomoles of Vitamin B12: Electrocatalytic Nano-Impacts MethodSingle Vitamin B12 (VB12) nanodroplets are used to mediate the reduction of oxygen in neutral buffer (see picture). The mechanism of oxygen reduction mediated by single VB12 droplets is revealed as via both CoII and CoI reduced from CoIII in VB12 through one- or two-electron transfer followed by the four-electron reduction of oxygen.

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One-Step Synthesis of [16]Helicene

Kazuyuki Mori, Dr. Takashi Murase and Prof. Dr. Makoto Fujita

One-Step Synthesis of [16]HeliceneAn aromatic spiral layer: A [16]helicene core was prepared in a single step by sextuple photocyclization from a single-strand arylene–vinylene precursor containing four phenylene and three naphthylene units linked by six vinylene spacers. X-ray crystallographic analysis revealed the triple-layered structure. A new guideline for the design of precursor olefins resulted in the longest helicene synthesized to date.

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A Planarized Triphenylborane Mesogen: Discotic Liquid Crystals with Ambipolar Charge-Carrier Transport Properties

Dr. Tomokatsu Kushida, Ayumi Shuto, Prof. Dr. Masafumi Yoshio, Prof. Dr. Takashi Kato and Prof. Dr. Shigehiro Yamaguchi

A Planarized Triphenylborane Mesogen: Discotic Liquid Crystals with Ambipolar Charge-Carrier Transport PropertiesB planar, B aligned: A planarized triphenylborane, bearing three 3,4,5-tridodecyloxyphenyl groups, forms a hexagonal columnar liquid-crystalline phase at ambient temperature. It has a columnar π-stacked structure and ambipolar carrier-transport properties with hole- and electron-mobility values of 3×10−5 cm2 V−1 s−1 and approximately 10−3 cm2 V−1 s−1, respectively.

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High-Fidelity Noncovalent Synthesis of Hydrogen-Bonded Macrocyclic Assemblies

Carlos Montoro-García, Jorge Camacho-García, Dr. Ana M. López-Pérez, Nerea Bilbao, Sonia Romero-Pérez, Dr. María J. Mayoral and Dr. David González-Rodríguez

High-Fidelity Noncovalent Synthesis of Hydrogen-Bonded Macrocyclic AssembliesFine design of a dinucleoside monomer leads to hydrogen-bonded macrocyclic tetramer assemblies with high effective molarities and remarkable thermodynamic and kinetic stability. The behavior of these assemblies in various solvents is discussed.

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