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Structural Chemistry of Titanium (IV) Oxo Clusters, Part 2: Clusters Without Carboxylate or Phosphonate Ligands Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Ulrich Schubert, Berthold Stöger
Homometallic titanium oxo clusters (TOC) are one of the most important groups of metal oxo clusters. In a previous article, TOC structures with carboxylato and phosphonato ligands were reviewed and categorized. This work is now extended to clusters with other ligands. Comparison of the different cluster types shows how the interplay between condensation of the titanium polyhedra by means of bridging
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Directly‐Fused Ni(II)Porphyrin Conjugated Polymers with Blocked meso‐positions: Impact on Electrocatalytic Properties Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Deepak BANSAL, Hadi Ghahramanzadehasl, Drialys Cardenas-Morcoso, Jessica Desport, Gilles Frache, Giuseppe Bengasi, Nicolas D. Boscher
The oxidative coupling reaction of two Ni(II) porphyrins meso‐substituted with three and four phenyl groups, Ni(II) 5,10,15‐(triphenyl)porphyrin (NiPh3P) and Ni(II) 5,10,15,20‐(tetraphenyl)porphyrin (NiPh4P) respectively, was investigated in a oxidative chemical vapor deposition (oCVD) process. Irrespective of the number of meso‐substituents, high‐resolution mass spectrometry evidences the formation
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Perfect Polar Alignment of Parallel Beloamphiphile Layers: Improved Structural Design Bias Realized in Ferroelectric Crystals of the Novel “Methoxyphenyl Series of Acetophenone Azines” Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Harmeet Bhoday, Nathan Knotts, Rainer Glaser
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Understanding the Remarkable Stability of Well‐defined Dinuclear Copper(I) Carbene Complexes Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Roel Bienenmann, Marianne de Vries, Martin Lutz, Daniel Broere
The synthesis of a well‐defined dicopper carbene complex supported by the PNNP (2,7‐bis(di‐tert‐butylphosphaneyl)methyl‐1,8‐naphthyridine) expanded pincer ligand is reported. This carbene complex is remarkably stable, even in the presence of air and water. The reactivity of this complex was explored towards typical carbene transfer substrates and its electronic structure was investigated. Using a combination
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Enantioselective Synthesis of α‐Quaternary Isochromanes by Oxidative Aminocatalysis and Gold Catalysis Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Philipp Waser, Jonas Faghtmann, Marta Gil-Ordóñez, Anne Kristensen, Esben B. Svenningsen, Thomas B. Poulsen, Karl Anker Jørgensen
A novel strategy that combines oxidative aminocatalysis and gold catalysis allows the preparation of chiral α‐quaternary isochromanes, a motif that is prevalent in natural products and synthetic bioactive compounds. In the first step, α‐branched aldehydes and propargylic alcohols are transformed into α‐quaternary ethers with excellent optical purities (>90% ee) via oxidative umpolung with DDQ and an
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Opportunity of Patterning in Chemistry Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Denis Gentili, Massimiliano Cavallini
Patterning offers an efficient way to quantitatively enhance and enlarge material properties and functionalities, offering unprecedented opportunities for innovation in various scientific domains. By precisely controlling the spatial arrangement of materials at the micro‐ and nanoscale, patterning enables the exploitation of inherent material properties in novel ways. In addition, it generates new
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Steric effects on single‐molecule conductance in flat‐lying phenanthrene Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Kevin Batzinger, Qinghai Zhou, Xiang Ye, Eric Borguet, Shengxiong Xiao, Manuel Smeu
A previous combined experimental and theoretical study found that the position of anchoring groups on a phenanthrene (PHE) backbone played a large role in determining the single‐molecule conductance of the PHE derivative. However, a consistent 0.1 G0 feature was found across all PHE derivatives. To understand this, the previously investigated PHE derivatives were placed flat on a simulated Au substrate
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Fluorescence and Lifetime Imaging of Endoplasmic Reticulum Polarity Change During Ferroptosis Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Mingfeng Li, Yuncong Chen, Weijiang He, Zijian Guo
As a new form of regulated cell death, ferroptosis is closely related to various diseases. Tracing ferroptosis related biological behavior is helpful to better understand this process and its related biology. Considering that ferroptosis is featured with remarkable lipid peroxidation which can easily change the membranes’ compositions and structures, it is potential to detect intracellular environmental
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Energy Barrier and Gaps between Two Excited States in a Dual‐Emissive Carborane Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Xueyuan Zhao, Xining Zhang, Xin Li, Lin Wu, Lei Ji
A thorough understanding of the internal conversion process between excited states is important for designing ideal multiple emissive materials. However, it is hard to experimentally measure both the energy barrier and energy gaps between the excited states of a compound. For a long time, it is dubious if what was measured is the energy gap or energy barrier between two excited states. In this paper
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Post‐formation of fused pentagonal structure on fjord region of polyaromatic hydrocarbons under hydrothermal conditions Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Naoto Hamaguchi, Takumi Kubota, Masaaki Yamada, Hikaru Kimura, Hayato Tsuji
This study explores the synthesis of cyclopenta‐fused polyaromatic hydrocarbons (CP‐PAHs) via Pt‐catalyzed cyclization in water, focusing on the formation of fused pentagonal rings within heavily fused PAH frameworks. Utilizing platinum catalysts at lower temperatures (200‐260°C) in water, led to the successful synthesis of singly cyclized CP‐PAHs. The reaction conditions facilitated the mono‐cyclization
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Selective B(3)‐H activation without auxiliary reagents affording multinuclear Ir(III) complexes with (o‐carboranyl)dithioester ligands Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Yong-Xiao Zhu, Run-Ze Yuan, Hai-Ning Zhang, Guo-Xin Jin
A method was developed to link two or three o‐carborane moieties to form a series of carboranyl dithioester bridging ligands via in situ substitution of haloalkanes by tetraphenylphosphonium carboranyldithiocarboxylates. Based on these ligands, direct B‐H activation without the assistance of Ag(I) and alkali was successfully achieved with half‐sandwich Ir(III) substrate [Cp*IrCl2]2 to yield corresponding
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Ion Mobility Mass Spectrometry‐based Disaccharide Analysis of Glycosaminoglycans Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Lukasz Polewski, Eunjin Moon, Andreas Zappe, Michael Götze, Gergő Péter Szekeres, Christian Roth, Kevin Pagel
Glycosaminoglycans (GAGs) are linear and acidic polysaccharides. They are ubiquitous molecules, which are involved in a wide range of biological processes. Despite being structurally simple at first glance, with a repeating backbone of alternating hexuronic acid and hexosamine dimers, GAGs display a highly complex structure, which predominantly results from their heterogeneous sulfation patterns. The
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A Structure‐Activity Investigation of the Fungal Metabolite (‐)‐TAN‐2483B: Inhibition of Bruton’s tyrosine kinase. Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Jordan McCone, Paul H. Teesdale-Spittle, Jack U. Flanagan, Joanne E. Harvey
The natural product (‐)‐TAN‐2483B is a fungal secondary metabolite which displays promising anti‐cancer and immunomodulatory activity. Our previous syntheses of (‐)‐TAN‐2483B and sidechain analogues uncovered inhibitory activity against Bruton’s tyrosine kinase (Btk), an established drug target for various leukaemia and immunological diseases. A structure‐based computational study using ensemble docking
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Current Developments in Emerging Lanthanide‐doped persistent luminescent scintillators and their applications Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Huiru Ye, Yantao Li, Xukai Chen, Weidong Du, Longfei Song, Yu Chen, Qiuqiang Zhan, Wei Wei
Lanthanide‐doped scintillators have the ability to convert the absorbed X‐ray irradiation into ultraviolet (UV), visible (Vis), or near‐infrared (NIR) light. Lanthanide‐doped scintillators with excellent persistent luminescence are emerging as a new class of persistent luminescent materials recently. They have attracted great attention due to their unique "self‐luminescence" characteristic and potential
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Pyrene Functionalized Norbornadiene‐Quadricyclane Fluorescent Photoswitches: Characterization of their Spectral Properties and Application in Imaging of Amyloid Beta Plaques Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Shima Ghasemi, Monika Shamsabadi, Axel Olesund, Andreas Erbs Hillers-Bendtsen, Francisco Najera, Fredrik Edhborg, Adil S. Aslam, Wera Larsson, Zhihang Wang, Francoise M. Amombo Noa, Rebecca J. Salthouse, Lars Öhrström, Helen Hölzel, Ezequiel Perez-Inestrosa, Kurt V. Mikkelsen, Jörg Hanrieder, Bo Albinsson, Ambra Dreos, Kasper Moth-Poulsen
This study presents the synthesis and characterization of two fluorescent norbornadiene (NBD) photoswitches, each incorporating two conjugated pyrene units. Expanding on the limited repertoire of reported photoswitchable fluorescent NBDs, we explore their properties with a focus on applications in bioimaging of amyloid beta (Aβ) plaques. While the fluorescence emission of the NBD decreases upon photoisomerization
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Continuous Synthesis of a Macrocyclic Sulfite of Polyethylene Glycol by Cascaded Continuous Stirred Tank Reactors (CSTRs) Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Jichang Wei, Yinli Liu, Yuchen Sun, Jun Bai, He Gao, Zhaojun Yang, Long Pan
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Fagopyrins from Buckwheat Flowers: Structural and Stereochemical Characterization through Combined NMR/CD Spectroscopy and Theoretical Calculations. Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Valerio Galbusera, Benedetta Lattuada, Andrea Pinto, Alberto Barbiroli, Gigliola Borgonovo, Enzio Maria Ragg
Fagopyrins are phenantroperylenequinones present in the flowers of Fagopyrum esculentum (buckwheat) endowed with photodynamic activity. It has been reported that fagopyrin extracts actually contain a complex mixture of closely related compounds, differing only on the nature of the perylenequinone substituents. We report our systematic and detailed study on the chemical composition of fagopyrin extracts
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Tetraanionic Oligo‐Dioxaborines: Strongly Absorbing Near‐Infrared Dyes Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Vladyslav Polishchuk, Andrii Kulinich, Mykola Shandura
Polymethine dyes of tetraanionic nature comprising 1,3,2‐dioxaborine rings in the polymethine chain and end‐groups of different electron‐accepting abilities have been synthesized. They can be considered as oligomeric polymethines, where a linear conjugated π‐system passes through three 1,3,2‐dioxaborine units and a number of tri‐ and dimethine π‐bridges between two end‐groups. The obtained dyes exhibit
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Engineering Modular DNA Reaction Networks for Signal Processing Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Shuang Cui, Xin Liu, Xun Zhang, Peijun Shi, Yanfen Zheng, Bin Wang, Qiang Zhang
Diversified molecular information‐processing methods have significant implications for nanoscale manipulation and control, monitoring and disease diagnosis of organisms, and direct intervention in biological activities. However, as an effective approach for implementing multifunctional molecular information processing, DNA reaction networks (DRNs) with numerous functionally specialized molecular structures
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A Highly Sterically Encumbered Boron Lewis Acid Enabled by a Organotellurium‐based Ligand Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Daniel Wegener, Alberto Pérez-Bitrián, Niklas Limberg, Anja Wiesner, Kurt F. Hoffmann, Sebastian Hasenstab-Riedel
Lewis acidic boron compounds are ubiquitous in chemistry due to their numerous applications, yet tuning and optimizing their properties towards different purposes is still a challenging field of research. In this work, the boron Lewis acid B[OTeF3(C6F5)2]3 was synthesized by reaction of the teflate derivative HOTeF3(C6F5)2 with BCl3 or BCl3·SMe2. This new compound presents a remarkably high thermal
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Synthesis Strategies, Preparation Methods, and Applications of Chiral Metal‐Organic Frameworks Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Hui Zhang, Qingsong Cheng, Hebing Pei, Simin He, Ruibin Guo, Nijuan Liu, Zunli Mo
: Chiral metal‐organic framework (CMOFs) is a kind of material with great application value in recent years. Formed by the coordination of metal ions or metal clusters with organic ligands. It is widely used in chemistry, biology, medicine and materials science because of its ordered and adjustable pores, multi‐dimensional network structure, large specific surface area and excellent adsorption properties
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14‐Membered Macrocyclic β‐Diiminato Gold(II) – A New Member for the Gold(II) Complex Family? Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Lukas Sorge, Julian Link, Katja Heinze
The chemistry of molecular gold compounds is dominated by the oxidation states +I and +III. For the intermediate oxidation state +II with 5d9 electron configuration, dimerization or disproportionation of the gold(II) radicals is favoured, so that only a few mononuclear gold(II) complexes have been isolated to date. The present study addresses the one‐electron reduction of the macrocyclic gold(III)
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Exploring the Magnetic Interactions in Two Novel Cyanide‐bridged Homo‐ and Heterometallic Hexadecanuclear Complexes Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Jyoti Yadav, Arindam Gupta, Arpan Mondal, Florian Daumann, Gerald Hörner, Birgit Weber, Sanjit Konar
Two novel isostructural cyanide‐bridged hexadecanuclear complexes with the general formula {[Fe(CN)6]6[M{en(Bn)py}]10}2+ [M = Fe (12+), Ni (22+)] have been synthesized. The structural analyses disclose the presence of multivalent Fe centres with different spin states in complex 12+ whereas all the Fe centres share a conserved oxidation state in complex 22+. The DC magnetic study revealed antiferromagnetic
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One‐Pot Synthesis of Nanoflower‐Like Bimetallic Sulfides of Zn2SnS4 as Nanozymes for Highly Sensitive Sensing of H2O2 Released by Living Cells Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Xia Wen, Jiancong Ni, Shunmu Zeng, Zhiping Song, Weiwei Qiu
The sensitive and reliable nanozyme‐based sensor enables the detection of low concentrations of H2O2 in biological microenvironments, it has potential applications as an in‐situ monitoring platform for cellular H2O2 release. The uniformly dispersed bimetallic sulfide (Zn2SnS4) nanoflowers were synthesized via a one‐pot hydrothermal method and the two kinds of metal ions can serve as morphology and
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Effect of Co‐adsorbed Guest Adsorbates on the Separation of Ethylene/Ethane Mixtures on Metal‐Organic Frameworks with Open Metal Sites Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Yuqing Xiao, Shenhui Li, Bin Jiang, Xinmiao Liang, Yueying Chu, Feng Deng
Direct determination of the equilibrium adsorption and spectroscopic observation of adsorbent‐adsorbate interaction is crucial to evaluate the olefin/paraffin separation performance of porous adsorbents. However, the experimental characterization of competitive adsorption of various adsorbates at atomic‐molecular level in the purification of multicomponent gas mixtures is challenging but rarely conducted
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Application of Sublimation in the Synthesis and Crystal Growth of Organosulfones Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Lamis Alaa Eldin Refat, Jolanta Karpinska, Saidulu Konda, John M. Simmie, Paul Vincent Murphy, Patrick McArdle, Andrea Erxleben
The solvent‐free elimination of sulfinic acid and aromatization of 1,6‐trans‐substituted bis(arylsulfone) trienes is reported. It is shown that sublimation can be used as a ‘green’ method to combine the thermal transformation of six trienes and the crystal growth of the resulting 4‐(phenylsulfonyl)biphenyls. When the sublimation conditions are carefully controlled, high quality single crystals of the
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Catalytic Cascade: Efficient Synthesis of Cyclohepta[b]indoles and Cyclohepta[b]indole‐Indoline Conjugates via RCM, Hydrogenation, and Acid‐Catalyzed Ring Expansion Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Nabin Parui, Tirtha Mandal, Sandip Maiti, Jyotirmayee Dash
Cyclohepta[b]indoles, prevalent in natural products and pharmaceuticals, are conventionally accessed via metal or Lewis acid‐mediated cycloadditions with prefunctionalized substrates. Our study introduces an innovative sequential catalytic assembly for synthesizing cyclohepta[b]indoles from readily available isatin derivatives. The process involves three catalytic sequences: ring‐closing metathesis
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Variation in Catalytic Efficacies of a 2D pH‐stable MOF by Altering Activation Methods Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Janaki Behera, Arun Pal, Rupam Sahoo, Madhab C. Das
Although it is well‐known that the Lewis acidity of Metal‐Organic Frameworks (MOFs) can effectively enhance their catalytic activity in organic transformations, access to these Lewis‐acidic sites remains a key hurdle to widespread applications of Lewis‐acidic catalysis by MOFs. Easy accessibility of strong Lewis acidic sites onto 2D MOFs by using proper activation methods can be a cornerstone in attaining
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Multiple Bonding in AeN‐ (Ae = Ca, Sr, Ba) Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Li-juan Cui, Yu-qian Liu, Meng-hui Wang, Bing Yan, Sudip Pan, Zhong-hua Cui, Gernot Frenking
Quantum chemical calculations using ab initio methods at the MRCI+Q(8,9)/def2‐QZVPPD and CCSD(T)/def2‐QZVPPD levels as well as density functional theory are reported for the diatomic molecules AeN‐ (Ae = Ca, Sr, Ba). The nature of the bonds is analyzed with a variety of methods. The anions CaN‐ and SrN‐ have electronic triplet (3Π) ground states with nearly identical bond dissociation energies De ~57
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Selective Lattice Doping Enables a Low‐cost, High‐capacity and Long‐lasting Potassium Layered Oxide Cathode for Potassium and Sodium storage Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Ruopeng Ai, Xinyuan Zhang, Shuyue Li, Zhixuan Wei, Gang Chen, Fei Du
Layered transition metal oxides are highly promising host materials for K ions, owing to their high theoretical capacities and appropriate operational potentials. To address the intrinsic issues of KxMnO2 cathodes and optimize their electrochemical properties, a novel P3‐type oxide doped with carefully chosen cost‐effective, electrochemically active and multi‐functional elements is proposed, namely
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Synthesis of Calix[4]arene‐Based Porous Organic Cages and Their Gas Adsorption Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Qidi Kong, Lei-Lei Liu, Zhongyue Li
Two crystalline large‐sized porous organic cages (POCs) based on conical calix[4]arene (C4A) were designed and synthesized. The four‐jaw C4A unit tends to follow the face‐directed self‐assembly law with the planar triangular building blocks such as tris(4‐aminophenyl)amine (TAPA) or 1,3,5‐tris(4‐aminophenyl)benzene (TAPB) to generate a predictable cage with a stoichiometry of [6+8]. The formation of
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Reductions of Arenes using a Magnesium‐Dinitrogen Complex Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Matthew J. Evans, Jeremy Mullins, Rahul Mondal, Cameron Jones
In this contribution, we present “Birch‐type”, and other reductions of simple arenes by the potassium salt of an anionic magnesium dinitrogen complex, [{K(TCHPNON)Mg}2(μ‐N2)] (TCHPNON = 4,5‐bis(2,4,6‐tricyclohexylanilido)‐2,7‐diethyl‐9,9‐dimethyl‐xanthene), which acts as a masked dimagnesium(I) diradical in these reactions. This reagent is non‐hazardous, easy‐to‐handle, and readily provides access
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Dynamics of Coordinated Phosphonate Group Directly Observed by 17O‐NMR in Lanthanide(III) Complexes of a Mono(ethyl phosphonate) DOTA Analogue. Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Adam Svítok, Jan Blahut, Peter Urbanovský, Petr Hermann
Biological phosphates can coordinate metal ions and their complexes are common in living systems. Dynamics of mutual oxygen atom exchange in the tetrahedral group in complexes has not been investigated. Here, we present a direct experimental proof of the exchange (“phosphonate rotation”) in model Ln(III) complexes of monophosphonate H4dota analogue which alters phosphorus atom chirality of coordinated
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Classification and identification of perfume scents by an enantioselective colorimetric sensor array of chiral metal‐organic‐framework‐based Fabry‐Pérot films Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Kuo Zhan, Anemar Bruno Kanj, Lars Heinke
Many odors, like perfumes, are complex mixtures of chiral and achiral molecules where the cost‐efficient (enantio‐)selective sensing represents a major technical challenge. Here, we present a colorimetric sensor array of surface‐mounted metal‐organic‐framework (SURMOF) films in Fabry–Pérot (FP) cavities. The optical properties of the FP‐SURMOF films with different chiral and achiral structures are
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In Silico Design and Characterization of a New Molecular Electride: Li@Calix[3]Pyrrole Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Ranajit Saha, Bastian Bjerkem Skjelstad, Sudip Pan
Electrides, in which anionic electrons are localized independent of the atoms in the compound, have shown promise especially as catalysts and optoelectronic materials. Here, we present a new computationally designed molecular electride, Li@calix[3]pyrrole (Li@C3P). Electron density and electron localization function analyses unequivocally confirm the existence of localized electride electron density
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Azophosphines: Synthesis, Structure and Coordination Chemistry Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Emma J. Jordan, Ethan D. E. Calder, Holly V. Adcock, Louise Male, Martin Nieger, J. Chris Slootweg, Andrew R. Jupp
The conceptual replacement of nitrogen with phosphorus in common organic functional groups unlocks new properties and reactivity. The phosphorus‐containing analogues of triazenes are underexplored but offer great potential as flexible and small bite‐angle ligands. This manuscript explores the synthesis and characterisation of a family of air‐stable azophosphine‐borane complexes, and their subsequent
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Conformational and Electronic Variations in 1,2‐ and 1,6‐Cyclophellitols and Their Impact on Retaining α‐Glucosidase Inhibition Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Tim P. Ofman, Jurriaan J. A. Heming, Alba Nin-Hill, Florian Küllmer, Elisha Moran, Megan Bennett, Roy Steneker, Anne-Mei Klein, Gijs Ruijgrok, Ken Kok, Zach W. B. Armstrong, Johannes M. F. G. Aerts, Gijsbert A. van der Marel, Carme Rovira, Gideon J. Davies, Marta Artola, Jeroen D. C. Codée, Hermen S. Overkleeft
: Glycoside hydrolases (glycosidases) take part in myriad biological processes and are important therapeutic targets. Competitive and mechanism‐based inhibitors are useful tools to dissect their biological role and comprise a good starting point for drug discovery. The natural product, cyclophellitol, a mechanism‐based, covalent and irreversible retaining β‐glucosidase inhibitor has inspired the design
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B(C6F5)3/CPA‐Catalyzed Aza‐Diels–Alder Reaction of 3,3‐Difluoro‐2‐Aryl‐3H‐indoles and Unactivated Dienes Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Xing-Pin Wei, Xin-Chun Wang, Tao Ma, Xiu-Xiu Qiao, Ganpeng Li, Yonghui He, Xiao-Jing Zhao
Here we report B(C6F5)3/CPA‐catalyzed enantioselective aza‐Diels–Alder reaction of 3,3‐difluoro‐2‐Aryl‐3H‐indoles with unactivated dienes to access chiral 10,10‐difluoro‐tetrahydropyrido[1,2‐a]indoles. This protocol allows the formation of pyrazole‐based C2‐quaternary indolin‐3‐ones with high enantioselectivities and regioselectivities. Moreover, gram‐scale synthesis of the 10,10‐difluoro‐tetrahydropyrido[1
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Boosting Excited‐State Energy Transfer by Anchoring Dipole Orientation in Binary Thermally Activated Delayed Fluorescence/J‐Aggregate Assemblies Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-15 Zhuoming Ma, Zilong Guo, Yixuan Gao, Yaxin Wang, Min Du, Yandong Han, Zheng Xue, Wensheng Yang, Xiaonan Ma
Förster resonance energy transfer (FRET) has been widely applied in fluorescence imaging, sensing and so on, while developing useful strategy of boosting FRET efficiency becomes a key issue that limits the application. Except optimizing spectral properties, promoting orientation factor (κ2) has been well discussed but rarely utilized for boosting FRET. Herein, we constructed binary nano‐assembling
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Generation and Identification of the Trifluorosilylarsinidene F3SiAs and Isomeric Perfluorinated Arsasilene FAsSiF2 Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-15 Guohai Deng, Sebastian Hasenstab-Riedel
The trifluorosilylarsinidene F3SiAs in the triplet ground state has been generated through the reaction of laser‐ablated silicon atoms with AsF3 in cryogenic Ne‐ and Ar‐matrices. The reactions proceed with the initial formation perfluorinated arsasilene FAsSiF2 in the singlet ground state by two As‒F bonds insertion reaction on annealing. The trifluorosilylarsinidene F3SiAs was formed via F‐migration
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Tuning the Emission Properties of 2,1,3‐Benzothiadiazoles via Regioselective Substitution Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-15 Mauricio Posada Urrutia, Christine Dyrager
The 2,1,3‐benzothiadiazole (BTD) unit is a prominent building block commonly used in various research areas such as optoelectronics and bioimaging. Despite its great versatility, the development of strategies to elaborate BTD has been largely neglected, including exploring its reactivity and understanding how regioselective functionalization can be used to tune the fluorescence emission. Previous focus
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Investigation of Isolated IrF5−, IrF6− Anions and M[IrF6] (M = Na, K, Rb, Cs) Ion Pairs by Matrix‐Isolation Spectroscopy and Relativistic Quantum‐Chemical Calculations Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-15 Yan Lu, Artur Wodyński, Marc Reimann, Robert Medel, Martin Kaupp, Sebastian Hasenstab-Riedel
The molecular IrF5−, IrF6− anions and M[IrF6] (M = Na‐Cs) ion pairs were prepared by co‐deposition of laser‐ablated MF with IrF6 and isolated in solid Ne or Ar matrices. The free anions were obtained by co‐deposition of IrF6 with laser‐ablated metals (Ir, Pt) as electron sources. The products were characterized in a combined analysis of matrix IR spectroscopy and electronic structure calculations using
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Opportunities of MXenes in Heterogeneous Catalysis. V2C as Aerobic Oxidation Catalyst Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-15 Amarajothi Dhakshinamoorthy, Rubén Ramizrez-Grau, Hermenegildo García, Ana Primo
MXenes are 2D nanomaterials having alternating sheets of one atom‐thick early transition metal layer and one atom‐thick C or N layer. The external surface contains termination groups, whose nature depends on the etching agent used in the preparation procedure from the MAX phase. The present concept proposes that, due to their composition, the metal‐surface termination groups make MXenes particularly
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The Formation of Carbon Dots from D‐Glucose Studied by Infrared Spectroscopy Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-15 Livia Fois, Luigi Stagi, Davide Carboni, Meera Alboushi, Abbas Khaleel, Roberto Anedda, Plinio Innocenzi
Carbon dots (C‐dots) obtained from D‐glucose have attracted great interest because of their properties and as a model for understanding the synthesis process and the origin of photoluminescence in carbon‐based nanostructures. Synthesising C‐dots under hydrothermal conditions has become one of the most common methods for their preparation. Understanding the details of this process is quite difficult
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Controlling Diastereoselectivity in Dearomatizing Diels‐Alder Reactions of Nitroarenes with 2‐Trimethylsilyloxycyclohexadiene Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-15 Marian Powderly, Mélanie Roseau, Gilles Frison, David Harrowven, Julien Legros, Isabelle Chataigner, Rayane Hammami, Laetitia Chausset-Boissarie
Dearomative Diels‐Alder cycloadditions between nitroarenes and 2‐trimethylsilyloxycyclohexadiene are carried out under high pressure at room temperature in the absence of any chemical promoter. Reactions are performed with different arenes, including the highly aromatic naphthalenes and quinolines. They lead to 3D‐scaffolds with exquisite exo‐diastereoselectivity. The exo approach is characterized
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Radiation‐Induced Defects in Uranyl Trinitrate Solids Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-15 Samantha Kruse, Harindu Rajapaksha, Jay LaVerne, Sara Mason, Tori Forbes
Actinides are inherently radioactive; thus, ionizing radiation is emitted by these elements can have profound effects on its surrounding chemical environment through the formation of free radical species. While previous work has noted that the presence of free radicals in the system impacts the redox state of the actinides, there is little atomistic understanding of how these metal cations interact
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Perfect Polar Alignment of Parallel Beloamphiphile Layers: Improved Structural Design Bias Realized in Ferroelectric Crystals of the Novel “Methoxyphenyl Series of Acetophenone Azines” Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-15 Harmeet Bhoday, Nathan Knotts, Rainer Glaser
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Two Hydroxyfluorooxoborates Achieving Deep‐ultraviolet Cutoff Edges and Moderate Birefringence by Assembling Multi‐anionic Groups Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-15 Huanhuan Cheng, Xiaojing Li, Shilie Pan, Zhihua Yang
Assembling multi‐anionic groups is conducive to utilizing respective advantage to achieve the enhancement of optical performance. Two new hydroxyfluorooxoborates, Rb2B3O3F4(OH) and K8Cs2B15O14(OH)7F20·H2O with [B3O3F4(OH)] six‐membered rings were synthesized for the first time. The title compounds exhibit short ultraviolet cutoff edges (< 200 nm) and K8Cs2B15O14(OH)7F20·H2O possesses a moderate experimental
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Regioselective Synthesis of Hamilton‐Receptor‐Fullerene Oligo‐Adducts for the Supramolecular Binding of Cyanuric Derivatives Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-15 Michael Wachter, Barbara Scholz, Erik Schulze, Frank Hampel, Eugenia Pérez-Ojeda, Andreas Hirsch
A new concept for the regioselective synthesis of Hamilton‐receptor and cyanurate‐functionalized oligo adducts of the fullerene C60 was developed. Based on an in‐situ deprotection and click‐post‐functionalization approach with novel azido precursors, the corresponding fullerene hexakis‐adducts with octahedral addition patterns and up to twelve Hamilton‐receptor/cyanurate moieties surrounding the fullerene
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Near‐Infrared‐II Nanomaterials for Activatable Photodiagnosis and Phototherapy Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-13 Wanying Jiang, Lisheng Lin, Ping Wu, Hongxin Lin, Jian Sui
Near‐Infrared‐II (NIR‐II) spans wavelengths between 1,000 to 1,700 nanometers, featuring deep tissue penetration and reduced tissue scattering and absorption characteristics, providing robust support for cancer treatment and tumor imaging research. This review explores the utilization of activatable NIR‐II photodiagnosis and phototherapy based on tumor microenvironments (e.g., reactive oxygen species
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Surface Engineering of the Mechanical Properties of Molecular Crystals via an Atomistic Model for Computing the Facet Stress Response of Solids Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-13 Mubarak Almehairbi, Vikram C. Joshi, Ahamad Irfan, Zeinab M Saeed, Tamador Alkhidir, Aya M Abdelhaq, Praveen B Managutti, Bhausaheb Dhokale, Thaksen Jadhav, Changquan Calvin Sun, Sharmarke Mohamed
Dynamic molecular crystals are an emerging class of crystalline materials that can respond to mechanical stress by dissipating internal strain in a number of ways. Given the serendipitous nature of the discovery of such crystals, progress in the field requires advances in computational methods for the accurate and high‐throughput computation of the nanomechanical properties of crystals on specific
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Total Chemical Synthesis of Aggregation‐Prone Disulfide‐Rich Starfish Peptides Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-13 Hongkang Wu, Praveen Praveen, Thomas NG Handley, Chaitra Chandrashekar, Scott F. Cummins, Ross A. D. Bathgate, Mohammed Akhter Hossain
: A relaxin‐like gonad‐stimulating peptide (RGP), Aso‐RGP, featuring six cysteine residues, was identified in the Crown‐of‐Thorns Starfish (COTS, Acanthaster cf. solaris) and initially produced through recombinant yeast expression. This method yielded a single‐chain peptide with an uncleaved C‐peptide (His Tag) and suboptimal purity. Our objective was to chemically synthesize Aso‐RGP in its mature
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Defect Induced Structural Transition and Lipase Immobilizatoin in Mesoporous Aluminum Metal‐Organic Frameworks Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-13 Sivasankar Kulandaivel, Chun-Chuen Yang, Yi-Chun Yeh, Chia-Her Lin
The disorder to order and structural transformation are unique metal‐organic framework (MOF) characters. How to adapt or control both behaviors in MOF is rarely studied. In this case, we demonstrate that our successful synthesis of [Al(OH)(PDA)]n (AlPDA‐53‐DEF, AlPDA‐53‐H, and AlPDA‐68) with H2PDA = 4,4'‐[1,4‐phenylenebis(ethyne‐2,1‐diyl)]‐di benzoic acid has illuminated the intricate world of Aluminum
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Unidentical Twins: Geometrically Similar but Chemically Distinct Metal‐free Sites in Boron Oxide for Methane Oxidation to HCHO, CO and CO2 Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-12 Parveen Rawal, Puneet Gupta
Metal‐free boron‐based catalysts such as boron oxide (B2O3) and boron nitride (h‐BN) are promising catalysts for the methane oxidation to HCHO and CO. The B2O3 catalyst contains various probable boron sites (B1 to B6), which may be responsible for methane oxidation. In this work, we utilized density functional theory to compare two relevant geometrically identical boron sites (B2 and B4) for their
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Silver(i) Perfluoroalcoholates: Synthesis, Structure, and their Use as Transfer Reagents Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-12 Paul Golz, Kamar Shakeri, Lilian Maas, Marius Balizs, Alberto Pérez-Bitrián, Helen D. Kemmler, Merlin Kleoff, Patrick Voßnacker, Mathias Christmann, Sebastian Hasenstab-Riedel
Herein we report a general access to silver(i) perfluoroalcoholates, their structure in the solid state and in solution, and their use as transfer reagents. The silver(i) perfluoroalcoholates are prepared by the reaction of AgF with the corresponding perfluorinated carbonyl compounds in acetonitrile and are stable for a prolonged time at –18 °C. X‐Ray analysis of single crystals of perfluoroalcoholate
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Metal‐Organic Framework PCN‐224 Combined Cobalt Oxide Nanoparticles for Hypoxia Relief and Synergistic Photodynamic / Chemodynamic Therapy Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-12 Haoming Yuan, Kaixiu Chen, Jing Geng, Ziyong Wu, Chao Wang, Pengfei Shi
Photodynamic therapy (PDT) and chemodynamic therapy (CDT) are promising tumor treatments mediated by reactive oxygen species (ROS), which have the advantages of being minimally invasive. However, the hypoxia of tumor microenvironment and poor target ability often reduce the therapeutic effect. Here we propose a tumor targeted nanoplatform PCN‐224@Co3O4‐HA for enhanced PDT and synergistic CDT, constructed
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Continuous Synthesis of a Macrocyclic Sulfite of Polyethylene Glycol by Cascaded Continuous Stirred Tank Reactors (CSTRs) Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-12 Jichang Wei, Yinli Liu, Yuchen Sun, Jun Bai, He Gao, Zhaojun Yang, Long Pan
Invited for the cover of this issue is the group of Long Pan and co‐workers at Asymchem Life Sciences (Tianjin) Co. Ltd. The image depicts a novel continuous process for the synthesis of a macrocyclic poly(ethylene glycol) (PEG) sulfite, the precursor to PEG macrocyclic sulfate, a useful building block in PEG chemistry. Read the full text of the article at 10.1002/chem.202304319.
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Polydentate Amidinato‐Silylenes, ‐Germylenes and ‐Stannylenes Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-12 Javier A. Cabeza, Pablo García-Álvarez
This review article focuses on amidinatotetrylenes that potentially can (or have already shown to) behave as bi‐ or tridentate ligands because they contain at least one amidinatotetrylene moiety (silylene, germylene or stannylene) and one (or more) additional coordinable fragment(s). Currently, they are being widely used as ligands in coordination chemistry, small molecule activation and catalysis
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Formation, Selective Encapsulation, and Tautomerization Control of Isoindoleone Utilizing Guanidinium Sulfonate Framework Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-12 Mohammad T. Chaudhry, Justin A. Newman, Alfred Y. Lee
Herein we report the use of tetrakis(guanidinium) pyrenetetrasulfonate (G4PYR) and bis(guanidinium) 1,5‐napthalene disulfonate (G2NDS) to catalyze the cyclization of 2‐cyanobenzamide (1) to isoindolone (2). Moreover, we demonstrate the remarkable selectivity of these guanidinium organosulfonate hosts in encapsulating 2 over 1. By thoroughly investigating the intramolecular cyclization reaction, we
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Trapping an Elusive Phosphanyl‐Phosphaalumene Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-12 Lilian S. Szych, Lars Denker, Joey Feld, Jose Goicoechea
We describe our attempts to access a compound with an Al=P double bond by reaction of Al(Nacnac) towards [H2CN(Dipp)]2PPCO (Nacnac = HC[C(Me)N(Dipp)]2; Dipp = 2,6‐iPr2C6H3). Our observations are consistent with the formation of a transient phosphanyl‐phosphaalumene at low temperatures (−70 °C), however this species was found to readily undergo intramolecular C–H activation of the β‐diketiminato ligand