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An Efficient and Scalable “Second Generation” Total Synthesis of the Marine Polyketide Limaol Endowed with Antiparasitic Activity Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-08 Stephan N. Hess, Alois Fürstner
The cluster of four skipped exo-methylene substituents on the “northern” wing of limaol renders this marine natural product unique in structural terms. This arguably non-thermodynamic array gains kinetic stability by populating conformations which impede isomerization to a partly or fully conjugated polyene. This analysis suggested that the difficulties encountered in our first total synthesis had
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Unusual Stability of an end-on Superoxido Copper(II) Complex under Ambient Conditions Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-08 Chiara Eleonora Campi, Konstantinos Parkatzidis, Athina Anastasaki, Siegfried Schindler
Superoxido copper complexes play an important role as usually short-lived intermediates in biology and chemistry. The unusual stability of an end-on superoxido copper complex observed in an oxygen-enhanced atom transfer radical polymerization (ATRP) led to a detailed mechanistic investigation of the formation of [CuII(Me6tren)(O2•−)]+ (Me6tren = tris(2-dimethyl-aminoethyl)amine) under ambient conditions
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Chirality Sensing of Cryptochiral Guests with Prism[n]arenes Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-08 PAOLO DELLA SALA, Umberto Calice, Veronica Iuliano, Silvano Geremia, Neal Hickey, Sandra Belviso, Francesco Ferdinando Summa, Guglielmo Monaco, Carmine Gaeta, Stefano Superchi
Optical chirality sensing has gained significant attention in recent years. Within this field, the quest for stereodynamic chiroptical probes capable of detecting cryptochiral guests presents a formidable challenge. Macrocycles exhibiting planar chirality have emerged as promising candidates for amplifying the chirality of cryptochiral guests. In this study, we demonstrate that the formation of host-guest
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Visible-Light-Driven Germyl Radical Generation via EDA-Catalyzed ET–HAT Process Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-08 Kaito Yoshizawa, Bi-Xiao Li, Taro Matsuyama, Chao Wang, Masanobu Uchiyama
We have established a facile and efficient protocol for the generation of germyl radicals by employing photo-excited electron transfer (ET) in an electron donor-acceptor (EDA) complex to drive hydrogen-atom transfer (HAT) from germyl hydride (R3GeH). Using a catalytic amount of EDA complex of commercially available thiol and benzophenone derivatives, the ET-HAT cycle smoothly proceeds simply upon blue-light
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Photo-Induced Generation of Oxygenated Quaternary Centers via EnT Enabled Singlet O2 Addition to C3-Maleimidated Quinoxaline: A Reagent-Less Approach Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-08 Subhendu Ghosh, Tamanna Khandelia, Anjali Mahadevan, Pritishree Panigrahi, Piyush Kumar, Raju Mandal, Deepjyoti Boruah, Sugumar Venkataramani, Bhisma K Patel
Demonstrated here is an external photo-sensitizer-free (auto-sensitized) singlet oxygen-enabled solvent-dependent tertiary hydroxylation and aryl-alkyl spiro-etherification of C3-maleimidated quinoxalines. Such “reagent-less” photo-oxygenation at Csp3−H and etherification involving Csp3−H/Csp2−H are unparalleled. Possibly, the highly π-conjugated N−H tautomer allows the substrate to get excited by
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Ruthenium(II) polypyridyl complexes with benzoxazole derivatives and non-innocent ligands as effective antioxidants in human neuroblasts Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-08 Gina Elena Giacomazzo, Luca Conti, Daniele Paderni, Patrick Severin Sfragano, Lorenzo Quadrini, Eleonora Macedi, Camilla Andreini, Chiara Donati, Caterina Bernacchioni, Gloria Mulas, Barbara Valtancoli, Ilaria Palchetti, Luca Giorgi, Vieri Fusi, Francesca Cencetti, Claudia Giorgi
Ruthenium(II) polypyridyl complexes continue to raise increasing interest for the encouraging results in several biomedical areas. Considering their vast chemical-physical repertoire, in particular the possibility to switch from the sensitization of reactive oxygen species (ROS) to ROS-scavenging abilities by tuning the nature of their ligands, it is therefore surprising that their potential as antioxidants
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UoC-7: A Bimetallic K-Zn-MOF with an Anionic Framework Based on Fluorinated Trimesate Ligands Exhibiting a Large CO2 Uptake Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-08 Susanna Wenzel, Aimeé E. L. Cammiade, Ronja K. Christoffels, Sean S. Sebastian, Tim Mattick, Uwe Ruschewitz
In solvothermal reactions of Zn(NO3)2×6H2O with K(H2mF-BTC) or K(H2dF-BTC) in DMF/ethanol or DMA/ethanol solvent mixtures, single crystals of the MOFs UoC-7(1F) and UoC-7(2F) were obtained crystallizing in the hexagonal space group P63/m (no. 176) (H3BTC: 1,3,5-benzenetricarboxylic acid; mF-/dF: mono-/difluoro; DMF: N,N-dimethylformamide; DMA: N,N-dimethylacetamide; UoC: University of Cologne). According
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Mixed Tin Valence in the Tin(II/IV)-Nitridophosphate Sn3P8N16 Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-08 Sebastian J. Ambach, Aylin Koldemir, Kristian Witthaut, Sandra Kreiner, Thomas Bräuniger, Rainer Pöttgen, Wolfgang Schnick
Sn3P8N16 combines the structural versatility of nitridophosphates and Sn within one compound. It was synthesized as dark gray powder in a high-pressure high-temperature reaction at 800 °C and 6 GPa from Sn3N4 and P3N5. The crystal structure was elucidated from single-crystal diffraction data (space group C2/m (no. 12), a = 12.9664(4), b = 10.7886(4), c = 4.8238(2) Å, β = 109.624(1)°) and shows a 3D-network
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The Complete Assessment of Small Molecule and Peptidomimetic Inhibitors of Sortase A Towards Antivirulence Treatment Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-08 Jordi C. J. Hintzen, Helal Abujubara, Daniel Tietze, Alesia Tietze
This review covers the most recent advances in the development of inhibitors for the bacterial enzyme sortase A (SrtA). Sortase A (SrtA) is a critical virulence factor present ubiquitously in Gram-positive bacteria of which many are considered pathogenic. Sortases are key enzymes regulating bacterial adherence to host cells, by anchoring extracellular matrix-binding proteins to the bacterial outer
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Telescoped Flow Synthesis of Azacyclic Scaffolds Exploiting the Chromoselective Photolysis of Vinyl Azides and Azirines Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-08 Ruairi Crawford, Marcus Baumann
An efficient chromoselective photochemical process is presented for the synthesis of 2H-azirines and 1,3-diazabicylo[3.1.0]hex-3-enes from readily available vinyl azides. The method exploits continuous flow photochemistry to enable the safe consumption of the hazardous azide group and provides uniform irradiation using high-power LEDs at 365-450 nm. Additionally, a scaled telescoped process has been
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Post-synthetic Metalation on the Ionic TiO2 Surface to Enhance Metal-CO2 Interaction During Photochemical CO2 Reduction Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-07 Laxmikanta Kanti Mallick, Krishna Samanta, Biswarup Chakraborty
During the photochemical CO2 reduction reaction, CO2 adsorption on the catalyst’s surface is a crucial step where the binding mode of the [metal-CO2] adduct directs the product selectivity and efficiency. Herein, an ionic TiO2 nanostructure stabilized by polyoxometalates (POM), ([POM]x@TiO2), is prepared and the sodium counter ions present on the surface to balance the POMs’ charge are replaced with
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Advancements in Interfacial Engineering for Perovskite Light-Emitting Diodes Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-08 Jaeho Lee, Zixi Xie, Lianzhou Wang, Jingwei Hou
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A Voyage into Chemical Bonds and Aromaticity Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-07 A. J. Stasyuk, Jordi Poater, Henrik Ottosson
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Characterizing the oligomers distribution along the aggregation pathway of amyloid Aß1‐40 by NMR Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-07 Katiuscia Pagano, Lucia De Rosa, Simona Tomaselli, Henriette Molinari, Luca Domenico D'Andrea, Laura Ragona
This study delves into the early aggregation process of the Aβ1‐40 amyloid peptide, elucidating the associated oligomers distribution. Motivated by the acknowledged role of small oligomers in the neurotoxic damage linked to Alzheimer’s disease, we present an experimental protocol for preparing 26‐O‐acyl isoAβ1‐40, a modified Aβ1‐40 peptide facilitating rapid isomerization to the native amide form at
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Ionic Porous Aromatic Frameworks Embedding Polyoxometalates for Heterogeneous Catalysis Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-07 Zhaofu Zhang, Yuhui Zhai, Mengnan Gu, Hengtao Lei, Yunxuan Li, Yue Li, Yuyang Tian, Guangshan Zhu
Porous aromatic frameworks (PAFs) are promising functional porous solids known for their feasible amenability and extraordinary stability. When the framework modified by ionic functional groups, the given ionic PAFs (iPAFs) exhibited charged channels for adsorption, separation and catalysis. However, the surface areas of ionic porous frameworks are usually lower than the neutral ones, and their synthesis
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Ytterbium(II) Complex‐Catalyzed Selective Single and Double Hydrophosphination of 1,3‐Enynes Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-07 Bing Jing, Cheng Zhu, Haibin Song, Jianfeng Li, Chunming Cui
1,3‐Enynes with the conjugated alkene and alkyne moieties are attractive building blocks in synthetic chemistry. However, neither 4,1‐hydrophosphination nor dihydrophosphination of 1,3‐enynes has been reported. In this paper, the divalent ytterbium and calcium amide complexes supported by silaimine‐functionalized cyclopentadiene ligands (C5Me4‐Si(L)=NR) were developed, which successfully catalyzed
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Synthesis of Diverse Allyl Sulfone Derivatives via Sequential Hydroalkoxylation of 1,3‐Enynes Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-07 Sourav Kumar, Bhahwal Ali Shah
A first metal‐free protocol for the synthesis of allylic sulfones featuring aldehyde functionality at the δ‐position has been reported. The formation of structurally complex δ,δ‐dimethoxy allyl sulfones is enabled by the direct nucleophilic attack of methoxide onto the sulfone‐containing 1,3‐enynes. The present approach allows facile installation of acetal groups within the allyl sulfone scaffold,
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Striking Borane Planarization in the Thermal Rearrangement (η5‐C5H5)Fe(η3‐B5H10) → (η5‐C5H5)Fe(η5‐B5H10) § Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-07 Josep M Oliva-Enrich, Maxime Ferrer, Ibon Alkorta, José Elguero, Julio Barrios, William Tiznado
In 1977 Weiss and Grimes, by means of mass spectrometry and 1H and 11B NMR spectroscopy, proposed two structures (I and II) for the ferraborane (η5‐C5H5)Fe(B5H10), isoelectronic with ferrocene. In this work, by means of high‐level quantum‐chemical computations, we confirm the experimental structures of the two isomers with their corresponding energies, and assign the reported 1H and 11B NMR chemical
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REASSIGNMENT OF THE STRUCTURE OF A TRYPTOPHAN‐CONTAINING CYCLIC TRIPEPTIDE PRODUCED BY THE BIARYLITIDE CROSSLINKING CYTOCHROME P450BLT Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-07 Laura J. Coe, Yongwei Zhao, Leo Padva, Angus Keto, Ralf Schittenhelm, Julien Tailhades, Greg Pierens, Elizabeth H. Krenske, Max Crüsemann, James De Voss, Max J. Cryle
The structure of the sidechain crosslinked Tyr‐Leu‐Trp peptide produced by the biarylitide crosslinking cytochrome P450Blt from Micromonospora sp. MW‐13 has been reanalysed by a series of NMR, computational and isotope labelling experiments and shown to contain a C‐N rather than a C‐O bond. Additional in vivo experiments using such a modified peptide show there is a general tolerance of biarylitide
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Silver‐Catalyzed Carbofluorination of Olefins and α‐Fluoroolefins with Carbamoyl Radicals Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-07 Émilie Vincent, Julien Brioche
The reactivity of carbamoyl radicals, generated in situ from sodium oxamate salts, has been investigated in the context of radical carbofluorination reactions of olefins and a‐fluoroolefins, respectively. Both transformations are catalyzed by silver salts and required the presence of potassium persulfate (K2S2O8) and SelectfluorTM as a radicophilic fluorine source. The reported methods provide a direct
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Stable Axially Chiral Cyclohexylidenes from Catalytic Asymmetric Knoevenagel Condensation Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-07 Meijia Ying, Kaixuan Wang, Wenjun Yan, Maoping Pu, Lili Lin
Axially chiral cycloalkylidenes are interesting but less developedaxially chiral molecules. Here, a bispidine‐based chiral amine catalytic system was developed to promote efficiently the asymmetric Knoevenagel condensation ofN‐protected oxindoles and benzofuranones with 4‐substituted cyclohexanones. A variety of alkylidenecycloalkanes with stable axial chirality were obtained in good yields with high
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Structure Engineering of Acridine Donor to Optimize Color Purity of Blue Thermally Activated Delayed Fluorescence Emitters Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-06 Yixuan Jiang, Jing Jin, Huicai Ren, Botao Liu, Yongqiang Mei, Min Xu, Di Liu, Jiuyan Li
9,9‐Dimethyl‐9,10‐dihydroacridine (DMAC) is one of the most widely used electron donor for constructing high‐performance thermally activated delayed fluorescence (TADF) emitters. However, DMAC‐based emitters often suffer from the imperfect color purity, particularly in blue emitters, due to its strong electron‐donating capability. To modulate donor strength, 2,7‐F‐Ph‐DMAC and 2,7‐CF3‐Ph‐DMAC were designed
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Biocompatible Synthesis of Macrocyclic Thiazol(in)e Peptides Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-06 Junming He, Christoph Nitsche
Macrocyclic peptides containing a thiazole or thiazoline in the backbone are considered privileged structures in both natural compounds and drug discovery, owing to their enhanced bioactivity, stability, and permeability. Here, we present the biocompatible synthesis of macrocyclic peptides from N‐terminal cysteine and C‐terminal nitrile. While the N‐terminal cysteine is incorporated during solid‐phase
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Tetrazole‐functionalized Organoboranes Exhibiting Dynamic Intramolecular N→B‐Coordination and Cyanide‐selective Anion Binding Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-06 Frank D. Pammer, Andreas Orthaber, Jonas Schepper
Starting from two different cyano‐functionalized organoboranes, we demonstrate that 1,3‐dipolar [3+2] azide‐nitrile cycloaddition can serve to generate libraries of alkyl‐tetrazole‐functionalized compounds capable of intramolecular NàB‐Lewis adduct formation. Due to the relatively low basicity of tetrazoles, structures can be generated that exhibit weak and labile NàB‐coordination. The reaction furnishes
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Spectroscopy and Photochemistry of [Al, N, C, O, H]: Connectivity to Aluminium‐Bearing Species in the Universe Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-06 Lina Wang, Xin Jiang, Beibei Sun, Tarek Trabelsi, Joseph S. Francisco, Xiaoqing Zeng, Mingfei Zhou
Aluminium is one of the most abundant metals in the universe and impacts the evolution of various astrophysical environments. Currently detected Al‐bearing molecules represent only a small fraction of the aluminium budget, suggesting that aluminium may reside in other species. AlO and AlOH molecules are abundant in the oxygen‐rich supergiant stars such as VY Canis Majoris, a stellar molecular factory
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Nitrogen Fixation by Manganese Complexes − Waiting for the Rush? Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-06 Quentin Le Dé, Dmitry A. Valyaev, Antoine Simonneau
Manganese is currently experiencing a great deal of attention in homogeneous catalysis as a sustainable alternative to platinum group metals due to its abundance, affordable price and low toxicity. While homogeneous nitrogen fixation employing well‐defined transition metal complexes has been an important area of research in coordination chemistry, manganese derivatives have been only sporadically used
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Polyaniline/Tungsten Trioxide Organic‐Inorganic Hybrid Anode for Aqueous Proton Batteries Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-06 Yuhao Tong, Yuan Wei, AJing Song, Yuanyuan Ma, Jianping Yang
Aqueous proton batteries have received increasing attention due to their outstanding rate performance, stability and high capacity. However, the selection of anode materials in strongly acidic electrolytes poses a challenge in achieving high‐performance aqueous proton batteries. This study optimized the proton reaction kinetics of layered metal oxide WO3 by introducing interlayer structured water and
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Hydrogen Tunneling Exhibiting Unexpectedly Small Primary Kinetic Isotope Effects Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-06 José P. L. Roque, Cláudio M. Nunes, Peter R. Schreiner, Rui Fausto
Probing quantum mechanical tunneling (QMT) in chemical reactions is crucial to understanding and developing new transformations. Primary H/D kinetic isotopic effects (KIEs) beyond the semiclassical maximum values of 7‒10 (room temperature) are commonly used to assess substantial QMT contributions in one‐step hydrogen transfer reactions, because of the much greater QMT probability of protium vs. deuterium
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Grain boundary defect engineering in rutile iridium oxide boosts efficient and stable acidic water oxidation Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-06 Ning Zhang, Ying-qi Fan, Depeng Wang, Yang Yu, Jianwei Liu, Jianrong Zeng, Di Bao, Haixia Zhong, Xin-bo Zhang
PEMWE is considered a promising technology for coupling with renewable energy sources to achieve clean hydrogen production. However, constrained by the sluggish kinetics of the anodic OER and the acidic abominable environment render the grand challenges in developing the active and stable OER electrocatalyst, leading to low efficiency of PEMWE. Herein, we develop the rutile‐type IrO2 nanoparticles
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Nanoproteases: Alternatives to Natural Protease for Biotechnological Applications Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-06 Yaru Wang, Mingxiu Guo, Xiaolong Xu
Some nanomaterials with intrinsic protease‐like activity have the advantages of good stability, biosafety, low price, large‐scale preparation and unique property of nanomaterials, which are promising alternatives for natural proteases in various applications. An especial term, "nanoprotease”, has been coined to stress the intrinsic proteolytic property of these nanomaterials. As a new generation of
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A Catalytic Approach for the Synthesis of Peptide–Oligonucleotides Conjugates in Aqueous Solution or On‐Column Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-06 Marion Gras, Pauline Adler, Michael Smietana
Peptide–oligonucleotide conjugates (POCs) are covalent architectures composed of a DNA or RNA molecules linked to a peptide. These constructs have found widespread applications ranging from hybrid nanomaterials to gene‐targeted therapies. Considering the important role of POCs, a new catalytic approach for their preparation is reported here, that could be applied either on solid support in anhydrous
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Synthesis and Performance of Bio‐Based Amphoteric Surfactants Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-06 Laura Maria Jansen, Pieter den Bakker, Niek Venbrux, Kim van Rijbroek, Dimphna Johanna Klaassen-Heshof, Wouter Lenferink, Sebastian Lücker, Adeline Ranoux, Harry Raaijmakers, Thomas Jan Boltje
As the global surfactant market continues to expand, there is an increasing need to develop bio‐based alternatives in the shift towards a circular economy. This study focuses on the synthesis of polar, amphoteric, amine‐oxide surfactants starting from biomass‐derived monosaccharides and demonstrating their potential in various applications. The synthesis involved a reductive amination of the sugars
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The Diversity and Evolution of Chiral Brønsted Acid Structures Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-06 Jasemine P. Handjaya, Niraja Patankar, Jolene Patricia Reid
The chemical space of chiral Brønsted acid catalysts is defined by quantity and complexity, reflecting the diverse synthetic challenges confronted and the innovative molecular designs introduced. Here, we detail how this successful outcome is a powerful demonstration of the benefits of utilizing both local structure searches and a comprehensive understanding of catalyst performance for effective and
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Epoxy Resins with Controllable "Thermally Conductive‐Self‐Healing" Synergies: a New Material to Meet the Needs of Flexible Electronic Devices Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-04 Jifeng Chen, Hui Xu, Zhu Mao, Kaixuan Nie, Yi Ning, Zhongyu Li, Bo Tian, Zhibo Sun, Pengli Zhu, Rong Sun
With the popularization of 5G technology and artificial intelligence, thermally conductive epoxies with self‐healing ability will be widely used in flexible electronic materials. Although many compounds containing both performances have been synthesized, there is little systematic theory to explain this coordination mechanism. In this paper, alkyl chains of different lengths were introduced to epoxies
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Synthesis, Characterization, and Cytotoxicity Evaluation of Novel Water‐Soluble Cationic Platinum(II) Organometallic Complexes with Phenanthroline and Imidazolic Ligands Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-04 Asjad Ali, Erika Stefàno, Federica De Castro, Giuseppe Ciccarella, Gianluca Rovito, Santo Marsigliante, Antonella Muscella, Michele Benedetti, Francesco P. Fanizzi
Platinum‐based chemotherapeutic agents are widely used in the treatment of cancer. However, their effectiveness is limited by severe adverse reactions, drug resistance, and poor water solubility. This study focuses on the synthesis and characterization of new water‐soluble cationic monofunctional platinum(II) complexes starting from the [PtCl(η1‐C2H4OEt)(phen)] (1, phen = 1,10‐phenanthroline) precursor
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New architecture based on Metal‐Organic Frameworks and spin crossover complexes to detect volatile organic compounds Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Emmelyne Cuza, Gilles Patriarche, Christian Serre, Antoine Tissot
We present here the encapsulation of a spin crossover complex C1 [FeII(L)] (L: 4‐amino‐, 2‐(2‐pyridinylmethylene)hydrazide) inside MOF‐808(Zr), a chemically robust Metal–Organic Framework. The compound C1⊂MOF‐808 retains its crystallinity as well as a partial porosity compared to pristine MOF and shows solvatochromism under Volatile Organic compounds (VOCs) sorption associated to a spin state change
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Alkene Cross−Metathesis with 2,5−Dimethyl−2,4−Hexadiene Enables Isobutylenyl / Prenyl Functionalizations and Rubber Valorization Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Paloma Mingueza−Verdejo, Silvia Rodríguez−Nuévalos, Judit Oliver−Meseguer, Antonio Leyva–Pérez
2,5−Dimethyl−2,4−hexadiene is a readily available and easily managable compound, whose symmetric and polymethylated dienic structure should be prone to engage in cross−metathesis reactions with other alkenes, but this has not been apparently exploited so far. Here we show that this reactant enables the easy synthesis of tri− and tetra−susbtituted alkenes (i.e. isobutylenyl and prenyl groups) from simple
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Poly(2‐oxazoline) Amphiphilicity Tunes the Excited‐State Proton Transfer of Pyrenol‐based Polyphotoacids Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Avinash Chettri, Leonid Kaberov, Niklas Klosterhalfen, Sandunika Perera, Mohammed Jamshied, Felix Schacher, Benjamin Dietzek-Ivansic
The ability of light to change the properties of light‐responsive polymers opens avenues for targeted release of cargo with a high degree of spatial and temporal control. Recently, we established photoacid polymers as light‐switchable macromolecular amphiphiles. In these systems, light‐induced excited‐state proton transfer (ESPT) causes changes in amphilicity. However, as the intermolecular process
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Unspecific Peroxygenase (UPO) can be Tuned for Oxygenation or Halogenation Activity by Controlling the Reaction pH Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Verity Barber, Tamara Mielke, Jared Cartwright, Alba Díaz-Rodríguez, William P. Unsworth, Gideon Grogan
Unspecific Peroxygenases (UPOs) are increasingly significant enzymes for selective oxygenations as they are stable, highly active and catalyze their reactions at the expense of only hydrogen peroxide as the oxidant. Their structural similarity to chloroperoxidase (CPO) means that UPOs can also catalyze halogenation reactions based upon the generation of hypohalous acids from halide and H2O2. Here we
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1,2,3‐Triazole‐containing azamacrocycles from chiral triazolopeptoids: synthesis and solid‐state studies Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Alicja Araszczuk, Giovanni Pierri, Rosaria Schettini, Chiara Costabile, Giorgio Della Sala, Luca Di Marino, Consiglia Tedesco, Francesco De Riccardis, Irene Izzo
Two new chiral 1,2,3‐triazole‐containing macrocyclic oligoamides (i.e.: triazolopeptoid 4 and 5) were obtained through solid‐phase synthesis of linear precursors followed by high dilution macrocyclization reaction. Theoretical (DFT) and spectroscopic (NMR) studies revealed the intricate interplay between the Na‐chiral side chains and their conformational attitudes. BH3‐mediated reduction of the tertiary
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Chiral Induction in a Self‐Assembled Pd4 Coordination Cage with Chiral Guests Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Raghunath Singha, Pankaj Maity, Dipak Samanta
The dynamic interplay of coordination bonds within metal‐organic cages offers a unique avenue for structural evolution in response to external stimuli, presenting a promising strategy for the construction of chiral assemblies. This adaptability is crucial for the selective synthesis of homochiral assemblies and advancement of asymmetric catalysis. In this study, we report the self‐assembly of an achiral
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Stereoselective Synthesis of Polysubstituted Dihydropyrroles via 1,5‐Addition and N‐1,4‐Addition Cascade Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Jing-Ming Zhang, Yu-Chao Wang, Liang Chen, Chao Ma, Zhi-Tao He
An unprecedented 1,5‐addition/N‐1,4‐addition cascade reaction is established via palladium hydride catalysis. A variety of polysubstituted dihydropyrrole skeletons are constructed in high yield and with exclusively >20:1 diastereoselectivity. An enantioselective protocol of this design is also developed to provide a novel access to enantioenriched dihydropyrroles.
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A Cu/MnOx Composite with Copper‐Doping‐Induced Oxygen Vacancies as a Cathode for Aqueous Zinc‐Ion Batteries Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Miao Han, Hongsheng Jia, Yubo Wang, Siqi Li, Yuanlong E, Yanqing Liu, Qingshuang Wang, Wanqiang Liu
Aqueous zinc‐ion batteries are anticipated to be the next generation of important energy storage devices to replace lithium‐ion batteries due to the ongoing use of lithium resources and the safety hazards associated with organic electrolytes in lithium‐ion batteries. Manganese‐based compounds, including MnOx materials, have prominent places among the many zinc‐ion battery cathode materials. Additionally
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Defect‐Engineered Metal–Organic Framework/Polyimide Mixed Matrix Membrane for CO2 Separation Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Samaneh Mashhadikhan, Abtin Ebadi, Mohamed Yasir Masoomi, Hamidreza Sanaeepur, Hermenegildo García
A novel defect‐engineered MOF (quasi ZrFum or Q‐ZrFum) was synthesized via a controlled thermal deligandation process and incorporated into a CO2‐philic 6FDA‐durene polyimide (PI) matrix to form Q‐ZrFum loaded MMMs. Defect‐engineered MOFs and fabricated MMMs were investigated in terms of their characteristic properties and separation performance. The incorporation of defects into the MOF structure
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Carbohydrate‐Functionalized Anthracene Carboximides as Multivalent Ligands and Bio‐Imaging Agents Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Anne George, Narayanaswamy Jayaraman
Anthracene carboximides (ACIs) conjugated with gluco‐, galacto‐ and mannopyranosides are synthesized, by glycosylation of N‐hydroxyethylanthracene carboximide acceptor with glycosyl donors. Glycoconjugation of anthracene carboximide increases the aq. solubility by more than 3‐fold. The glycoconjugates display red‐shifted absorption and emission, as compared to anthracene. Large Stokes shift (λabs/
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Controlling the Uptake and Release of Semiochemicals in Channel‐type Metal‐Organic Frameworks through Pore Expansion Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Joshua Nicks, Greig C. Shearer, Joseph Paul-Taylor, James Lai-Morrice, Chris Dadswell, Daniel Guest, William O. H. Hughes, John Spencer, Tina Düren, Andrew David Burrows
Semiochemicals can be used to manipulate insect behaviour for sustainable pest management strategies, but their high volatility is a major issue for their practical implementation. Inclusion of these molecules within porous materials is a potential solution to this issue, as it can allow for a slower and more controlled release. In this work, we demonstrate that a series of Zr(IV) and Al(III) metal‐organic
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Enhancing Control Over Nitric Oxide Photorelease via a Molecular Keypad Lock Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Hani M. Elbeheiry, Martin Schulz
Based on Boolean logic, molecular keypad locks secure molecular information, typically with an optical output. Here we investigate a rare example of a molecular keypad lock with a chemical output. To this end, the light‐activated release of biologically important nitric oxide from a ruthenium complex is studied, using proton concentration and photon flux as inputs. In a pH‐dependent equilibrium, a
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Vibrational Circular Dichroism of a Chiral Triplet Nitrene Investigated under Matrix‐Isolation Conditions in para‐Hydrogen Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Frederike Beyer, Corentin Grassin, Julien F. Rowen, Wolfram Sander, Christian Merten
VCD spectra of chiral high‐spin organic radicals are expected to show a strong intensity enhancement and are thought to be difficult to predict using state‐of‐the‐art theoretical methods. Herein we show that the chiral triplet nitrene obtained from photochemical cleavage of N2 from enantiopure 2‐azido‐9H‐fluorenol does not feature extraordinarily strong intensities and that the experimental spectra
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Organocatalyzed Asymmetric Conjugate Addition of Alcohols to β‐Fluoroalkyl Vinylsulfones by Bifunctional Phosphonium Salt Catalyst Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Xingjie Luo, Zhiyu Jiang, Siqun Yang, Xiaoyu Ren, Tianli Wang
Chiral secondary alcohols, serving as essential structural motifs, hold significant potential for diverse applications. The exploration of effective synthetic strategies toward these compounds is both attractive and challenging. Herein, we present an asymmetric oxa‐Michael reaction involving aliphatic alcohols as nucleophiles and β‐fluoroalkyl vinylsulfones catalyzed by bifunctional phosphonium salt
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Ring Fusion Elevates the Electronic Mobility of Azabenzannulated Perylene Diimide Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Fan Yang, Cui Wang, Laiyu Liang, Zhiqiang Wang, Xiaoxiao You, Guangwei Shao, Di Wu, Jianlong Xia
The backwardness of n‐type organic semiconductors still exists compared with the p‐type counterparts. Thus, the development of high‐performance n‐type organic semiconductors is of great importance for organic electronic devices and their integrated circuits. In recent years, azabenzannulated perylene diimide (PDI), as one of immense bay‐region‐annulated PDI derivatives, has drawn considerable attentions
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A GFP Inspired 8‐Methoxyquinoline‐Derived Fluorescent Molecular Sensor for the Detection of Zn2+ by Two‐Photon Microscopy Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Attila Csomos, Miklós Madarász, Gábor Turczel, Levente Cseri, Andrea Bodor, Anett Matuscsák, Gergely Katona, Ervin Kovács, Balázs Rózsa, Zoltán Mucsi
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High‐Pressure Synthesis of Cobalt Polynitrides: Unveiling Intriguing Crystal Structures and Nitridation Behavior Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Huawei Chen, Maxim Bykov, Iskander G. Batyrev, Lukas Brüning, Elena Bykova, Mohammad F. Mahmood, Stella Chariton, Vitali B. Prakapenka, Timofey Fedotenko, Hanns‐Peter Liermann, Konstantin Glazyrin, Andrew Steele, Alexander F. Goncharov
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Synthesis, Reactivity, and Complexation with Fe(0) of a Tight‐Bite Bis(N‐heterocyclic silylene) Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Zohreh Hendi, Madhusudan K. Pandey, Katharina Rachuy, Mukesh K. Singh, Regine Herbst‐Irmer, Dietmar Stalke, Herbert W. Roesky
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Unrevealing the Nitrogen Elusive Chirality of 3‐Sulfanyl and 3‐Sulfinyl N‐Tosyl Isoindolinones by ECD Spectra: An Experimental and Theoretical Investigation Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-03 Laura Palombi, Marta Monti, Erica Scarel, Valerio Morlacci, Mauro Stener, Massimiliano Aschi
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Gaining Insights into the Interplay between Optical and Magnetic Properties in Photoexcited Coordination Compounds Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-02 Jonas Braun, Annie K. Powell, Andreas Neil Unterreiner
We describe early and recent advances in the fascinating field of combined magnetic and optical properties of inorganic coordination compounds and in particular of 3d‐4f single molecule magnets. We cover various applied techniques which allow for the correlation of results obtained in the frequency and time domain in order to highlight the specific properties of these compounds and the future challenges
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Interaction of C60 with methylammonium lead iodide perovskite surfaces: Unveiling the Role of C60 in Surface Engineering Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-02 Gibu George, Sergio Posada Pérez
Understanding the interaction between fullerene (C60) and perovskite surfaces is pivotal for advancing the efficiency and stability of perovskite solar cells. In this study, we investigate the adsorption behavior of C60 on methylammonium lead iodide (MAPbI3) surfaces using periodic density functional theory calculations. We explore various surface terminations and defect configurations to elucidate
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Tunable Optical Anisotropy in Rare‐earth Borates with Flexible [BO3] Clusters Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-02 Xiangyu Long, Ran An, Yan Lv, Xueyan Wu, Miriding Mutailipu
Borates have garnered a lot of attention in the realm of solid‐state chemistry due to their remarkable characteristics, in which the synthesis of borates with isolated [BO3] by adding rare‐earth elements is one of the main areas of structural design study. Five new mixed‐metal Y‐based rare‐earth borates, Ba2ZnY2(BO3)4, KNa2Y(BO3)2, Li2CsY4(BO3)5, LiRb2Y(BO3)2, and RbCaY(BO3)2, have been discovered
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Oriented Metal‐organic Framework Membranes for Molecular Separations Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-02 Yanwei Sun, Yi Liu
Metal‐organic framework (MOF) membranes, which are recognized as state‐of‐the‐art platforms applied in various separation processes, have attracted widespread attention. Nonetheless, to overcome the trade‐off between permeability and selectivity, which is crucial for achieving efficient separation, it is important to rationally design and manipulate MOF membrane structure. Given remarkable advances
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RuPHOX‐Ru Catalyzed Asymmetric Cascade Hydrogenation of 3‐Substituted Chromones for the Synthesis of Corresponding Chiral Chromanols Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-02 Shaofeng Xu, Wenqi Xu, Siqi Dong, Delong Liu, Wanbin Zhang
An efficient RuPHOX‐Ru catalyzed asymmetric cascade hydrogenation of 3‐substituted chromones has been achieved under mild reaction conditions, affording the corresponding chiral 3‐substituted chromanols in high yields with excellent enantio‐ and diastereoselectivities (up to 99% yield, >99% ee and >20:1 dr). Control reactions and deuterium labelling experiments revealed that a dynamic kinetic resolution
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Synthesis of Indolines via Base‐Mediated C–H Activation and Defluorinative C–N Coupling, with no Need for Transition‐Metals Chem. Eur. J. (IF 4.3) Pub Date : 2024-05-02 Christian Weindl, Lukas Hintermann
Syntheses of (partially) aromatic nitrogen heterocycles increasingly rely on transition‐metal catalyzed C–C‐ and C–N‐cross‐coupling reactions. Here we describe a different approach to the synthesis of indolines by a domino C(sp3)–H activation, 1,2‐addition, and defluorinative SNAr‐cyclization sequence to provide the target 1,2‐diarylindolines (1,2‐diaryl‐2,3‐dihydroindoles) from ortho‐fluorinated methyl‐arenes