ArtikelGe32Co9−x: Creating “Empty” Space by High Pressurevon William P. et al. · 16.03.2023 The metastable phase Ge32Co9−x has been synthesized at high-pressure and temperature. It adopts a new structure type with three-core heteroclusters and unique chemical bonding. Units of three condensed cubes interconnect by sharing vertices and edg...
ArtikelSelectivity Rule of Cryptands for Anions: Molecular Rigidity and Bonding Sitevon Jiayao Li et al. · 16.03.2023 The cryptand cages with either −NH or −CH groups were computationally studied to identify their differences and determine the factors governing the anion preference. While the electrostatic interaction plays the predominating role in the capturing o...
ArtikelProbing Peptidylprolyl Bond cis/trans Status Using Distal 19F NMR Reportersvon Patrick M. et al. · 16.03.2023 It is demonstrated that incorporation of 4-fluorophenylalanine in model peptides provides an accurate and non-biased reporter of peptidylprolyl cis-trans conformational status by 19F NMR at physiological pH, even when several residues away from prol...
Artikell‐Serine is the Direct Precursor for the Pyrazine Ring Construction in the Biosynthesis of 3‐Isobutyl‐2‐Methoxypyrazine in Bell Pepper Fruits (Capsicum annuum L.)von Francesca Zamolo et al. · 16.03.2023 The biosynthetic pathway of 3-isobutyl-2-methoxypyrazine (IBMP) was investigated in plants using in vivo feeding experiments with stable-isotope labeled precursors. It has been demonstrated that photorespiratory derived l-serine serves as a C2-buili...
ArtikelExploiting Coordination Behavior of 7‐Azaindole for Mechanistic Investigation of Chan‐Lam Coupling and Application to 7‐Azaindole Based Pharmacophoresvon Krishanu Mondal et al. · 16.03.2023 Using a new copper(II)-DBU catalytic system, Chan-Lam type N-arylation of 7-azaindole is discussed. A new mechanism confirming the involvement of Cu(II)/Cu(III)/Cu(I) species for the cross-coupling pathway is proposed by identifying and characterizi...
ArtikelSynthesis of a B‐Antigen Hexasaccharide, a B‐Lewis b Heptasaccharide and Glycoconjugates Thereof to Investigate Binding Properties of Helicobacter pylorivon Mark Reihill et al. · 16.03.2023 Introduction of the Gal-α-(B)-determinant into a versatile Lacto-N-tetraose precursor followed by mono- or difucosylation afforded, after deprotection, the B-Lewis b heptasaccharide and the B-hexasaccharide structures, which were conjugated to BSA t...
ArtikelEffect of Mini‐PEGs Modification on the Enzymatic Digestion of D‐Amino Acid‐Containing Peptides under the Action of PROK von Liang Yan et al. · 16.03.2023 A series of mini-PEGs modified D-amino acid-containing peptides were synthesized. It was determined that the polyethylene glycol (PEG) modification promoted the enzymatic cleavage of the D-amino acid-containing peptides under the action of serine-li...
ArtikelC−C and C−N Bond Activation, Lewis‐Base Coordination and One‐ and Two‐Electron Oxidation at a Linear Aminoborylenevon Robert Witte et al. · 16.03.2023 An isolable linear aminoborylene: A dicoordinate cyclic alkyl(amino)carbene (CAAC)-stabilized aminoborylene isoelectronic with an allene undergoes intramolecular C−C bond activation under photolytic conditions, intramolecular aryl migration in the p...
ArtikelSpecific Signal Enhancement on an RNA‐Protein Interface by Dynamic Nuclear Polarizationvon Victoria Aladin et al. · 16.03.2023 A guide to better spectra: Dynamic nuclear polarization, sparse isotope labeling, and methyl dynamics have been combined to yield site-specific enhancement of NMR spectroscopic signals from the protein-RNA binding site within a ribonucleoprotein. Fo...
ArtikelDiverse Cooperative Reactivity at a Square Planar Aluminium Complex and Catalytic Reduction of CO2von Chloe L. et al. · 16.03.2023 Structural constraint imparted by a sterically demanding pincer ligand results in an unusual tetracoordinate aluminium Lewis acid that undergoes multiple modes of metal-ligand cooperative reactivity with ketones and CO2. Adding HBpin allows for the ...
ArtikelAsymmetrical Platinum and Rhodium Dinuclear Complex Strongly Bound to Filled d Complexes by Unbridged Pt−Metal Bonds: Toward Heterometallic‐Extended Metal Atom Chainsvon Kazuhiro Uemura et al. · 16.03.2023 Line up, line up! HOMO-LUMO interactions between metal d orbitals were used to synthesize hetero-xtended metal atom chains (EMACs) for tuning the number of nuclei and metal species. Mixing an asymmetrical Pt−Rh dinuclear complex with a LUMO in the ...
ArtikelPd/Co Catalyst with High Pd Atom Utilization Efficiency for Nitrobenzene Hydrogenation at Room Temperature: Experimental and DFT Studiesvon Jingwen Luo et al. · 16.03.2023 Put to good use: A Pd-doped Co (Pd/Co) catalyst with high Pd atom utilization efficiency was designed and prepared for hydrogenation of nitroarenes. Its catalytic activity was much better than commercial Pd powder (>150 times) in nitrobenzene hyd...
ArtikelCover Feature: Ge32Co9−x: Creating “Empty” Space by High Pressure (Chem. Eur. J. 16/2023)von William P. et al. · 16.03.2023 Essential structural features of the high-pressure phase Ge32Co9−x : The atomic arrangement is built from a uniquely distorted cubic primitive arrangement of Ge atoms. Ordered occupation of neighboring cubes by Co atoms forms heteroatomic three-core...
ArtikelCover Feature: Asymmetrical Platinum and Rhodium Dinuclear Complex Strongly Bound to Filled d Complexes by Unbridged Pt−Metal Bonds: Toward Heterometallic‐Extended Metal Atom Chains (Chem. Eur. J. 16/2023)von Kazuhiro Uemura et al. · 16.03.2023 Heterometallic trinuclear or pentanuclear complexes aligned as Rh−Pt−M or Rh−Pt−M−Pt−Rh (M=Pt, Pd, Cu), respectively, were kinetically and thermodynamically synthesized and characterized. These polynuclear complexes, in which three kinds of metals f...
ArtikelFrontispiece: Detection of the Dark States in Thermally Activated Delayed Fluorescence (TADF) Process of Electron Donor‐Acceptor Dyads: Insights from Optical Transient Absorption Spectroscopyvon Xue Zhang et al. · 16.03.2023 Unraveling the complicated photophysics of thermally activated delayed fluorescence (TADF) compounds is not a trivial task, although it is critical to improve the performance of TADF emitters in OLED. In the Review by Zhao and colleagues (DOI: 10.10...
ArtikelFront Cover: Specific Signal Enhancement on an RNA‐Protein Interface by Dynamic Nuclear Polarization (Chem. Eur. J. 16/2023)von Victoria Aladin et al. · 16.03.2023 Like bright stars in a dark sky, sparsely 13C-labeled methyl groups in the protein domain “illuminate” the binding pocket of a ribonucleoprotein (RNP) complex for specific solid-state NMR spectroscopy of the interaction surface by localized transfer...
ArtikelFrontispiece: CRISPR/Cas‐Based MicroRNA Biosensorsvon Qian Zhang et al. · 16.03.2023 MiRNAs are important post-transcriptional regulators, and accurate detection of miRNAs is essential to disease diagnosis, therapy, and prognosis. In this review, we focus on the recent advance in CRISPR/Cas-integrated miRNA biosensors based on fluor...
ArtikelCRISPR/Cas‐Based MicroRNA Biosensorsvon Qian Zhang et al. · 16.03.2023 The construction of efficient biosensors for miRNA assay is essential for disease diagnosis, therapy, and prognosis. CRISPR/Cas system possesses high fidelity, precise localization capability, and efficient cleavage activity, making it attractive in...
ArtikelSpecific Signal Enhancement on an RNA–Protein Interface by Dynamic Nuclear Polarizationvon Victoria Aladin et al. · 16.03.2023 “In our study, we combined biochemical sparse isotope-labeling techniques, a unique DNP method, and well-established dipolar recoupling in order to create isolated polarization transfer chains that, for the first time, allow us to follow the polariz...
ArtikelA Playground for Heavy Atom Tunnelling: Neutral Substitutional Defect Rearrangement from Diamondoids to Diamondsvon Itzhak Sedgi et al. · 20.03.2023Many diamond properties are defined by substitutional defects (i.e. a carbon atom replaced by another element), which may involve the formation of structural isomers that can interconvert. Herein, we analysed by computational means the structure, the...
ArtikelBiomimetic Synthesis of Organic Molecular‐Doped Fluorescent Guanine Crystals with Pearlescencevon Dongmei Guo et al. · 20.03.2023Biomimetic synthesis of guanine crystals has been focused in the last years. However, multi-functional guanine crystals occluded with fluorescent molecules have not been realized in laboratory. Here, the controllable synthesis of guanine crystal micr...
ArtikelOrganic‐Inorganic Phenolic/POSS Hybrids Provide Highly Ordered Mesoporous Structures Templated by High Thermal Stability of PS‐b‐P4VP Diblock Copolymervon Ting-Chih Chou et al. · 18.03.2023Anionic living polymerization was used to prepare a diblock copolymer of poly(styrene-b-4-vinyl pyridine) (PS-b-P4VP), and a phenolic resin with a double-decker silsesquioxane (DDSQ) cage structure was used to form a phenolic/DDSQ hybrid (PDDSQ-30 wi...
ArtikelFormate additive for efficient and stable methylammonium‐free perovskite solar cells by gas‐quenchingvon Wenlong Song et al. · 18.03.2023In order to promote the commercialization of perovskite solar cells, gas-quenching is considered to be a promising technique for perovskite film fabrication. However, when handling with methylammonium-free (MA-free) perovskites, it is often difficult...
ArtikelSynthesis and Densification of Mo/Mg Co‐Doped Apatite‐type Lanthanum Silicate Electrolytes with Enhanced Ionic Conductivityvon Jing Li et al. · 18.03.2023 Introducing the Mo6+ and Mg2+ dopants into the lanthanum silicate structure can increase the amount of interstitial oxygen and improve the degree of densification at lower sintering temperatures and expand the migration channel of oxygen ions to imp...
ArtikelThiophosphinoyl‐Tethered Ylide‐Substituted Heavier Carbenes: Synthesis, Structures and Stabilitiesvon Mike Jörges et al. · 18.03.2023 The synthesis and structure analysis of a series of mono and diylide-substituted tetrylenes of type YEX and Y2E (E=Ge, Sn, Pb; X=Cl or Br) with a thiophosphosphinoyl-tethered ylide is reported. Their relative stabilities were determined by ylide tra...
ArtikelIn situ H2O2 Generation and Corresponding Pollutant Removal Applications: A Reviewvon Jiahui Ji et al. · 18.03.2023 This review aims to offer a full-scale lens to discuss recent developments including fundamental process, design principles, and performance for pollutants removal from three perspectives like photocatalysis, electrocatalysis, and chemical activatio...
ArtikelCarbonylmetallates as Versatile 2‐, 4‐ or 6‐Electron Donor Metalloligands in Transition‐Metal Complexes and Clusters: A Global Approachvon Noura Naili et al. · 18.03.2023 The structure of various heterometallic carbonyl clusters containing metals that do not follow typical electron-counting rules can be readily explained by considering their constitutive 18e metal carbonyl fragment [m]− as a pseudo-halide, also simil...
ArtikelOrganocatalytic Desymmetric Conjugate Addition to Cyclobutanone: An Enantio‐ and Diastereoselective Synthesis of [6,5,4]‐Fused Carbocyclesvon Shibaram Panda et al. · 18.03.2023 The first organocatalytic desymmetrisation of 3-substituted cyclobutanone through intramolecular cyclisation. This study allowed us to access the architecturally fascinating [6,5,4]-fused carbocyclic skeleton with excellent selectivities (up to >...
ArtikelPhase‐Dependent Long Persistent Phosphorescence in Coumarin‐Phosphine‐Based Coinage Metal Complexesvon Vanitha et al. · 17.03.2023A coumarin functionalized aminodiphosphine has been introduced as a bidentate ligand in coinage metal chemistry. Mono-, di- and trimetallic copper and silver complexes were synthesized by using this ligand. A hybrid character of the ligand led to com...
ArtikelCoexistence of Three Different Spin States in a Cyanido‐Bridged Trinuclear Iron(III) Complex with an Unusual Fe III to Ligand Charge Transfervon Yong He et al. · 17.03.2023We report a trinuclear iron(III) cyanido-bridged complex trans-[CpMe3FeIII(dppe)(CN)]2[FeIII(LN4)][PF6]4 (2[PF6]4) as the oxidation product of binuclear complex [CpMe3(dppe)FeIICN-FeIII(LN4)][PF6] (1[PF6]) (CpMe3 = 1, 2, 4-trimethyl-1,3-cyclo-pentadi...
ArtikelCaffeine biodegradation by cytochrome P450 1A2. What determines the product distributions?von Thirakorn Mokkawes et al. · 17.03.2023Caffeine is a natural compound found in plant seeds that after consumption by humans effects the central nervous system as well as the cardiovascular system. In general, the cytochrome P450 enzymes in the liver are involved in the biodegradation of c...
ArtikelStructural and synthetic insights on oxidative homocouplings of alkynes mediated by alkali‐metal manganatesvon Pasquale Mastropierro et al. · 17.03.2023Exploiting bimetallic cooperation alkali-metal manganate(II) complexes can efficiently promote oxidative homocoupling of terminal alkynes furnishing an array of conjugated 1,3-diynes. The influence of the alkali-metal on these C-C bond forming proces...
Artikelλ3‐ and λ5‐Iodanes: Substituent Effects and Pseudorotation/ Hypervalent Twistingvon Keshaba et al. · 17.03.2023Hypervalent iodine (III and V) compounds exhibit positional isomerization through pseudorotation or twisting; the latter have been invoked for the stability as well as the reactivities of λ3- and λ5-iodanes. By judicious exploitation of sterics, the ...
ArtikelAcenaphthoimidazolylidene‐Ligated Palladacycle Enabled Suzuki‐Miyaura Cross‐Coupling Employing Equimolar Organoboron for Tri‐Ortho‐Substituted Bi(hetero)aryls and Terarylsvon Kun Wang et al. · 17.03.2023The Pd-catalyzed Suzuki-Miyaura cross-couplings (SMRs) are utilized as the most practical method to construct C-C bond, especial for biaryls. However, a major disadvantage of current protocols is the requirement of excess organoboron coupling partner...
ArtikelUnveiling Photodegradation and Photosensitization Mechanisms of Unconjugated Pterinsvon Enrique Manuel et al. · 17.03.2023Unconjugated pterins are ubiquitous molecules participating in countless enzymatic processes and potentially involved in the photosensitization of singlet oxygen, amino acids, and nucleotides. Following electronic excitation with UV-A light, some of ...
ArtikelA Multiresponsive Calix[6]arene Pseudorotaxane Empowered by Fluorophoric Dansyl Groupsvon Leonardo Andreoni et al. · 17.03.2023 A multiresponsive pseudorotaxane, composed by a dansyl calix[6]arene and a bipyridinium axle, is presented. The disassembly of this complex can be triggered by: i) protonation of the dansyl units (chemical stimulus); ii) electrochemical reduction of...
ArtikelAutomated Glycan Assembly of Mycobacterial Hexaarabinofuranoside and Docosasaccharide Arabinan (Araf23) Motifs found on Mycobacterium tuberculosisvon Narayana Murthy et al. · 17.03.2023 Automated assembly of oligo-arabinoses proves access to important tools useful in studying the cell surface of mycobacterium tuberculosis. Key to a robust process is protected orthogonal thiofuranoside building blocks that will be helpful for the sy...
ArtikelIntermetallic Compound TiM (M = Co, Fe) with a Layered Structure Prepared by Deoxidizing Ilmenite‐type Oxides in Molten LiCl–CaH2 Mixturesvon Yasukazu Kobayashi et al. · 17.03.2023CsCl-type intermetallic compounds TiM (M = Co, Fe) were obtained by deoxidizing trigonal ilmenite-type MTiO3 with a reducing agent CaH2 in molten LiCl at 600°C. X-ray diffraction, nitrogen adsorption, scanning electron microscopy, and transmission el...
ArtikelC versus O Protonation in Zincate Anions: A Simple Gas‐Phase Model for the Surprising Kinetic Stability of Organometallicsvon Rene Rahrt et al. · 17.03.2023 Why do organozinc reagents survive instantaneous protolysis in protic media? A gas-phase model shows that the protonation of the organyl group, although thermodynamically strongly favored, is outcompeted by the protonation of a hydroxy ligand. Abs...
ArtikelDynamic Metalloporphyrin‐Based [2]Rotaxane Molecular Shuttles Stimulated by Neutral Lewis Base and Anion Co‐ordinationvon Jamie et al. · 16.03.2023A series of dynamic metalloporphyrin [2]rotaxane molecular shuttles comprising of bis-functionalised Zn(II) porphyrin axle and pyridyl functionalised macrocycle components are prepared in high yield via active metal template synthetic methodology. Ex...
ArtikelTransformation of the Cyclo‐P5 Middle Deck in [(Cp*Fe)(Cp’’’Co)(µ,η5:η4‐P5)] upon Functionalization – A Comprehensive Study of Reactivityvon Sabrina Dinauer et al. · 16.03.2023[(Cp*Fe)(Cp’’’Co)(µ,η 5 :η 4 -P5)] (1) was functionalized by main group nucleophiles and subsequently electrophilically quenched or oxidized. Reacting 1 with group 14 nucleophiles revealed different organo-substituted P5R middle-decks depending on th...
ArtikelInverting the Electronic Structure of Diylidylgermylenes by Backbone Modificationvon V. S. et al. · 16.03.2023Owing to the strong electron-donating ability of ylide substituents, diylidyltetrylenes are usually highly nucleophilic species with strong donor capacities. Here, we demonstrate that their electronic properties are in fact highly flexible and can be...
ArtikelIron‐Catalyzed Deoxynitrogenation of Carboxylic Acids with Cyanamides to Access Nitrilesvon Mengsheng Li et al. · 16.03.2023Efficient strategies to access nitriles from common organic functionalities are highly important, given their significance in synthetic and medicinal chemistry. Although the direct transformation of carboxylic acids to nitriles have been explored for...
ArtikelQuantitative Electromerism of a Well‐defined Mononuclear Copper Complex Through Reversible Intramolecular Metal‐Ligand Electron Transfervon Johanna Osterbrink et al. · 16.03.2023Copper amine oxidases are enzymes that exhibit in their active site a mononuclear copper complex and a 2,4,5-trihydroxyphenylalanine quinone (TPQ) cofactor; in the oxidative half of the catalytic cycle, the enzymes regulate their activity by a temper...
ArtikelSilver‐based Terpyridine Complexes as Antitumor Agentsvon María Gil-Moles et al. · 16.03.2023Silver complexes bearing substituted terpyridine or tetra-2-pyridinylpyrazine ligands have been prepared and structurally characterised. The study of the anticancer properties of silver complexes with this type of ligands is scarce, despite the possi...
ArtikelIonic liquid‐mediated approach for the synthesis of site‐specific thioether conjugatesvon Helal Abujubara et al. · 16.03.2023Site-specific conjugation approaches are of great importance in drug discovery, notably for the synthesis of biochemical probes or molecular conjugates for targeted delivery. Herein, we report a mild ionic liquid (IL)-mediated thiolation technique th...
ArtikelAlkoxyphosphorane/Borane Cooperative Alkylations: A Frustrated Lewis Pair Version of the Mitsunobu Reactionvon Ting Chen et al. · 16.03.2023 Alkoxyphosphoranes, Ph2P(OR)(O2C6Cl4) and the borane B(C6F5)3 generate zwitterions which act as FLPs to effect the alkylation of nucleophiles affording C−C, C−N, C−H and C−Cl coupling products. A DFT study confirms these reactions proceed via FLP ac...
ArtikelSynthesis of Sterically Encumbered Alkaline‐Earth Metal Amides Applying the In Situ Grignard Reagent Formationvon Simon Sengupta et al. · 16.03.2023 Magnesium and calcium are too inert to deprotonate amines directly. In addition, N-bound trialkylsilyl groups proved to be beneficial for the synthesis of calcium bis(amides). The addition of hydryl bromides or iodides to suspensions of calcium and ...
ArtikelPentafluorophenol (C6F5OH) Catalyzed Pictet‐Spengler Reaction: A facile and Metal‐free Approach Towards Tetrahydro‐β‐carbolinesvon Rina Mahato et al. · 16.03.2023Herein, we have disclosed pentafluorophenol as an operative catalyst for synthesizing (spirocyclic) tetrahydro-β-carbolines via the Pictet-Spengler reaction. This straightforward catalytic protocol works under mild conditions resulting indole alkaloi...
ArtikelResidue‐selective C−H sulfenylation enabled by acid‐activated S‐acetamidomethyl cysteine sulfoxide with application to one‐pot stapling and lipidation sequencevon Kento Ohkawachi et al. · 16.03.2023A tyrosine (Tyr)- or tryptophan (Trp)-selective metal-free C−H sulfenylation reaction using an acid-activated S-acetamidomethyl cysteine (Cys) sulfoxide, Cys(Acm)(O), has been achieved. The dually protonated intermediate produced from the Cys(Acm)(O)...
ArtikelDevelopment of the Safe and Broad‐Spectrum Aldehyde and Ketoamide Mpro inhibitors Derived from the Constrained α, γ‐AA Peptide Scaffoldvon Lei Wang et al. · 15.03.2023SARS-CoV-2 is still wreaking havoc all over the world with surging morbidity and high mortality. The main protease (Mpro) is essential in the replication of SARS-CoV-2, enabling itself an active target for antiviral development. Herein, we reported t...
ArtikelA Late‐Stage Aryl C‐H Olefination Strategy and Its Application Towards Global Proteome Profiling of ∆8‐Tetrahydrocannabinolvon Ying-Jie Lim et al. · 15.03.2023Drugs and bioactive natural products exert their pharmacological effects by engaging numerous cellular targets in our body. Identification of these protein targets is essential for understanding the mechanism-of-action of these compounds, thus contri...
ArtikelTuning Directed Photooxidation‐Induced Conversion of Pyrrole‐Based Styryl Coumarin Dual‐Color Photoconvertersvon Lazare Saladin et al. · 15.03.2023 “Our result showed that N-substitution of the converters’ pyrrole moiety could drive impressive changes in their photo-transformation properties.” This and more about the story behind the front cover can be found in the article at 10.1002/chem.20220...
ArtikelNanoscale probing of the supramolecular assembly in a two‐component gel by near‐field infrared spectroscopyvon Romain Chevigny et al. · 15.03.2023The design of soft biomaterials requires a deep understanding of molecular self-assembly. We introduce here a nanoscale infrared (IR) spectroscopy study of a two-component supramolecular gel to assess the system´s heterogeneity and supramolecular ass...
ArtikelPhotocatalytic Aerobic Cyclization of N‐Propargylamides Enabled by Selenium‐π‐Acid Catalysisvon Yong-Hao Wang et al. · 15.03.2023A dual catalytic approach combining photocatalyst and selenium-π-acid synergy has been used to cyclized of N-propargylamides. This method offers readily access to oxazole aldehydes under chemical oxidant-free conditions with low catalyst loadings, wh...
ArtikelExchange Interactions and Magnetic Properties of a Molecular Mn18‐Ring Complexvon Jascha Bandemehr et al. · 15.03.2023[Mn3O(OAc)7(HOAc)]6·xAcOH (x = 6–9) represents a rare example of a compound containing molecular Mn18-rings. These are formed by Mn3(µ3-O) subunits in which the high-spin Mn(III) centers are bridged by three pairs of acetate anions (AcO−). An AcOH mo...
ArtikelOxanorbornene‐Fused Phenazine–Pyrene Scaffolds with Different Configurationsvon Liping Ye et al. · 15.03.2023New molecular scaffolds of C-, Z- and box-shaped configurations are constructed by fusing phenazine and pyrene units with oxanorbornene. As revealed by X-ray crystallography, the C-shaped molecules exhibit two interesting π-π stacking modes of phenaz...
ArtikelBioactivities of Triazolium‐Based N‐Heterocyclic Carbene Saltsvon Jia Song et al. · 15.03.20231,2,4-Triazolium salts are precursors of N-heterocyclic carbenes (NHCs), which have been extensively used as effective catalysts and ligands for both asymmetric and non-enantioselective reactions. Nevertheless, they are also a kind of quaternary ammo...
ArtikelElectronic Structure and Aromaticity of an Unusual Cyclo[18]carbon Precursor, C18Br6von Xia Wang et al. · 15.03.2023Herein, the electronic structure and bonding character of the stable cyclo[18]carbon (C18) precursor, C18Br6, are thoroughly characterized by molecular orbital (MO), density of states (DOS), bond order (BO), and interaction region indicator (IRI) ana...
ArtikelDe‐risking S‐F bond formation:A gas cylinder‐free strategy to access S(IV) and S(VI) fluorinated compounds.von Reza Kordnezhadian et al. · 14.03.2023The sulfur-fluorine partnership occupies a privileged position in fluorine chemistry given the functional versatility that it imparts to organic structures. Despite this, available methodologies to forge S–F bonds are limited compared to C–F bond for...
ArtikelHydrogen Bonding Parameters by Rapid Colorimetric Assessment: Evaluation of Structural Components Found in Biological Ligands and Organocatalystsvon Hanna et al. · 14.03.2023Hydrogen bonding is a key molecular interaction in biological processes, drug delivery, and catalysis. This report describes a high throughput UV-Vis spectroscopic method to measure hydrogen bonding capacity using a pyrazinone sensor. This colormetri...
ArtikelC−H Bond Activation Relay (CHAR) of Proline Ester Derivatives Promoted by In Situ Triarylamine Radical Cation: Selective Synthesis of 4‐Bromopyrrole Derivativesvon Han Ding et al. · 14.03.2023 A C−H activation relay (CHAR) of proline esters was realized by the in situ generated tris(4-bromophenyl)amine radical cation, selectively constructing the skeleton of 4-bromopyrrole under mild reaction conditions. Abstract Using the in situ gener...
ArtikelThe Aldol‐Tishchenko Reaction of Butanone, Cyclobutanone and a 3‐Pentanone Derived Sulfinylimine and DFT Calculations of the Stereo‐determining Stepvon Emma Alcock et al. · 14.03.2023 Enantio- and diastereoenriched 1,3-aminoalcohols are a highly versatile class of molecules in organic synthesis. However, most of the current syntheses involve a multi-step approach and the stepwise introduction of the chiral centres. Herein, we des...
ArtikelTris(boranil) Columnar Liquid Crystalline Fluorophores: pseudo‐Triphenylene Boron(III) Complexes with Peripheral N−B−O Linkagesvon B. N. et al. · 14.03.2023 Photoluminescent tris(boranil) discotics derived from tris-anils exhibit room temperature columnar mesomorphism, and redox behavior. Abstract The borate complexes derived from salicylaldimine ligands, called boranils, possess a wide range of photo...
ArtikelMesoporous CuFe2O4 Photoanodes for Solar Water Oxidation: Impact of Surface Morphology on the Photoelectrochemical Properties von Marcus Einert et al. · 14.03.2023 A systematic comparison of distinct surface morphologies of sol-gel-derived CuFe2O4 for solar water splitting shows that high-surface-area photoelectrodes are preferred for driving thermodynamically favorable reactions, such as sulfite oxidation, wh...
ArtikelTraceless N‐Polyfluoroalkylation of Weakly Nucleophilic Nitrogen Containing Compoundsvon Laura Santos et al. · 14.03.2023Here we report an efficient access to high-value N-polyfluoroalkyl anilines, primary polyfluoroalkylamines and N,N‑bis(polyfluoroalkyl)amines, via N‑polyfluoroalkylation of sulfonamides and phthalimide derivatives using sulfuryl fluoride (SO2F2). The...
ArtikelOxidation State Tuning of Room Temperature Phosphorescence and Delayed Fluorescence in Phenothiazine and Phenothiazine‐5,5‐dioxide Dimersvon Iain et al. · 14.03.2023Heterocyclic dimers consisting of combinations of butterfly-shaped phenothiazine (PTZ) and its chemically oxidized form phenothiazine-5,5-dioxide (PTZSO2) have been synthesized. A twist is imposed across the dimers by ortho-substituents including met...
ArtikelStructural complexity in the apparently simple crystal structure of Be2Ruvon Laura Agnarelli et al. · 14.03.2023The structural features of the hexagonal layered crystal structure of Be2Ru (a = 5.7508(3) Å, c = 3.0044(2) Å, space group P -62m) were investigated by single crystal X-ray diffraction and transmission electron microscopy (TEM). The residual electron...
ArtikelHAV‐peptides attached to colloidal probes faithfully detect E‐cadherins displayed on living cellsvon Silan Toy et al. · 14.03.2023Cell adhesion molecules are crucial for a variety of biological processes, including wound healing, barrier formationand tissue homeostasis. One of them is E-cadherin which is generally found at adherent junctions between epithelialcells. To identify...
ArtikelDiverse Roles of ScSERF in Modifying the Fibril Growth of Amyloidogenic Proteinsvon Chaozhe Wang et al. · 14.03.2023The aggregation of amyloidogenic proteins is often related to the occurrence of neurodegenerative diseases including fused in sarcoma protein (FUS) in frontotemporal lobar degeneration and amyotrophic lateral sclerosis diseases. Recently, the SERF pr...
ArtikelSpin in organic cocrystalsvon Cheng Zhang et al. · 14.03.2023Organic spintronics has caused a huge revolution in creating highly-efficient low-power circuits. Spin manipulation in organic cocrystals has become a promising strategy to uncover more chemicophysical properties for diverse applications. In this Min...
ArtikelNickel‐Catalyzed Regio‐ and Enantioselective Ring Opening of 3,4‐Epoxy Amides and Esters with Aromatic Aminesvon Jiawei Liu et al. · 14.03.2023Herein we present a nickel-catalyzed regio- and enantioselective ring opening reaction of 3,4-epoxy amides and esters with aromatic amines as nucleophiles. This method features high regiocontrol, diastereospecific SN2 reaction pathway, broad substrat...
ArtikelA Dynamic Approach to Synthetic Lectin for Glucose with Boosted Binding Affinity through C–H Hydrogen Bondsvon Canjia Zhai et al. · 13.03.2023A biomimetic receptor for glucose has been developed with high affinity and selectivity. The receptor was efficiently synthesized in three steps through dynamic imine chemistry followed by imine-to-amide oxidation. The receptor features two parallel ...
ArtikelElectrocarboxylation Reactions Using CO2 Both as Promoter and Carboxylative Reagentvon Ke Zhang et al. · 13.03.2023Electrocarboxylation reaction, which employs organic electrosynthesis to achieve the utilization of CO2 as a carboxylative reagent, provides a powerful and efficient tool for the preparation of organic carboxylic acid. In some electrocarboxylation re...
ArtikelQuest for a Rational Molecular Design of Alkyl‐Distyrylbenzene Liquid by Substitution Pattern Modulation von Xiao Zheng et al. · 13.03.2023 Via modulation of the substitution pattern, 2-decyltetradecyl chains at the 2,5-substituted position was found to be the desired substitution pattern for alkyl-distyrylbenzene liquids exhibiting the lowest viscosity as a practically stable liquid at...
ArtikelBreathing Behaviour Modification of Gallium MIL‐53 Metal–Organic Frameworks Induced by the Bridging Framework Inorganic Anionvon A. R. et al. · 13.03.2023 Controlling aspects of the μ2-X− bridging anion in metal-organic framework Ga-MIL-53 [GaX(bdc)] (X−=(OH)− or F−, bdc2−=terephthalate) can direct the conditions under which the breathing transition of this flexible framework occurs. Substituting 20 %...
ArtikelNovel Pyrimidine‐Based Iridium Complexes with Bulky Charge‐Carrier Groups as Dopants for Highly Efficient Green Polymer Light‐Emitting Diodesvon Gang Xie et al. · 13.03.2023Two new pyrimidine-based iridium complexes with triphenylamine and tetraphenylsilane, namely (TPAPr)2IrAcac and (TPSPr)2IrAcac, were fully synthesized and characterized. Both of the targeted iridium complexes exhibit excellent thermal stability and h...
ArtikelPd‐Bi bimetallic nanochains for electroredution of CO2 to syngas in ionic liquid‐based electrolytesvon Han Yang et al. · 13.03.2023Abstract: The electroreduction of carbon dioxide (CO2) is a sustainable method for generating valuable chemicals; however, avoiding unwanted hydrogen (H2) production during electrolysis is a major challenge. Coproduction of carbon monoxide (CO) and H...
ArtikelStructure Based Discovery of Inhibitors of CYP125 and CYP142 from Mycobacterium tuberculosisvon Mona et al. · 13.03.2023Mycobacterium tuberculosis (Mtb) was responsible for approximately 1.6 million deaths in 2021. With the emergence of extensive drug resistance, novel therapeutic agents are urgently needed, and continued drug discovery efforts required. Host-derived ...
ArtikelOne‐Pot Synthesis of Chiral 1‐Aryl‐2‐Aminoethanols via Ir‐Catalyzed Asymmetric Hydrogenationvon Lei Zhang et al. · 11.03.2023A straightforward synthesis approach to chiral 1-aryl-2-aminoethanols via the one-pot asymmetric hydrogenation catalyzed by Ir catalyst was developed. This tandem process involves the in situ generation of α-amino ketones via the nucleophilic substit...
ArtikelTriboelectric nanogenerators assembled by cobalt(II) coordination polymer incorporated composite films and their application for self‐powered anticorrosionvon Chao Huang et al. · 11.03.2023A friction layer with stability and durability is important to promote the practical application of triboelectric nanogenerators (TENGs). In this work, a two-dimensional cobalt coordination polymer (Co-CP) was successfully synthesized using cobalt ni...
ArtikelStereoselective Synthesis and Characterization of Indenone Azine‐Based Electron‐Accepting π‐Conjugated Systemsvon Shu et al. · 11.03.2023Indenone azines, in which the exocyclic C=C bond in dibenzopentafulvalene is replaced by an azine moiety (C=N–N=C), were synthesized as novel electron-accepting p-conjugated scaffolds. Structural modulation at the 7,7′-positions of indenone azines en...
ArtikelA BF2 Chelate Exhibiting Excimer‐like Fluorescence with an Unusually Large Stokes Shift in the Crystalline Phasevon Özgür Altan et al. · 10.03.2023The target mono-BF2 complex is weakly emissive in fluid solution because radiationless decay of the excited-singlet state is promoted through an intramolecular N…H–N hydrogen bond. The lack of mirror symmetry for this compound is attributed to vibron...
ArtikelControlled Shell and Kernel Modifications of Atomically Precise Pd/Ag Superatomic Nanoclustersvon Yu-Rong Ni et al. · 10.03.2023The first 8-electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg19(dtp)12] (dtp = S2P(O i Pr)2-) 1 and [PdHAg20(dtp)12]+2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of t...
ArtikelStructural Requirements of a Glycolipid MPIase for Membrane Protein Integrationvon Kohki Fujikawa et al. · 10.03.2023MPIase is a glycolipid involved in membrane protein integration in the inner membrane of Escherichia coli. To overcome the trace amounts and heterogeneity of natural MPIase, we systematically synthesized MPIase analogs. Structure-activity relationshi...
ArtikelSelective valorization of bio‐derived levulinic acid and its derivatives into hydrocarbons and biochemicals using hydrosilylationvon Nitish et al. · 10.03.2023Herein we report an efficient hydrosilylation strategy to selectively defunctionalize biomass-derived levulinic acid into value-added chemicals such as 1,4-pentanediol, 2-pentanol, 2-MTHF and C-5 hydrocarbons using cost-effective silanes and the comm...
ArtikelRationalizing the Optimization of Detergents for Membrane Protein Purificationvon Leonhard et al. · 10.03.2023Membrane protein purification by means of detergents is key to isolating membrane-bound therapeutic targets. The role of the detergent structure in this process, however, is not well understood. Detergents are optimized empirically, leading to failed...
ArtikelUse of Conglomerates Mixed Crystals to Deracemize a Stable Racemic‐Compound‐Forming Systemvon Clément Pinètre et al. · 10.03.2023Deracemization extended to racemic-compound-forming systems is demonstrated. We present here the first results of an alternative for the resolution of systems that exhibit a stable racemic compound but also a closely related conglomerate-forming syst...
ArtikelElemental Magnesium as an Early Transition Metal Substitute: From Pentafulvene Coordination to Deprotonation of Aminesvon Simon de et al. · 10.03.2023The reaction of magnesium turnings and 6,6-di-para-tolylpentafulvene was investigated. Under mild conditions, the magnesium dissolves, forming the MgII complex 1 with a π-η5:σ-κ1 coordinating ligand of the dimerized pentafulvene, analyzed by NMR and ...
ArtikelCombining Enantioselective Rh‐Catalyzed Conjugate Addition and Ir‐Catalyzed Allylic Alkylation in Stereodivergent, Multicomponent Coupling Reactions to Form Three Stereocentersvon Qiqige Qiqige et al. · 10.03.2023Stereodivergent dual catalysis has emerged as a powerful tool to selectively prepare all four stereoisomers in molecules containing two chiral centers from common starting materials. Most processes involve the use of two substrates, and it remains ch...
ArtikelSelective Construction Of Molecular Borromean Rings And [2]catenane Utilizing Ether Bipyridyl Ligandsvon Xin Yi et al. · 10.03.2023A series of Cp*Rh-based discrete architectures were constructed through selecting four ether bipyridyl ligands and three half-sandwich rhodium(III) bimetallic construction units, respectively. This study demonstrates a strategy for making the transit...
ArtikelRh‐Catalyzed Direct Decarbonylative Borylation of Carboxylic Acidsvon Chang Yin et al. · 10.03.2023Carboxylic acids are abundant, low cost and environmentally friendly, direct convert carboxylic acids into valued-added compounds are in high demand. Herein, we report a Rh(I) catalyzed direct decarbonylative borylation of aryl and alkyl carboxylic a...
ArtikelGraphene oxide‐BODIPY conjugates as bright fluorescent materialvon Giacomo Reina et al. · 09.03.2023Covalent functionalization of graphene oxide (GO) with boron dipyrromethenes (BODIPYs) was achieved through a facile synthesis, affording two different GO-BODIPY conjugates where the main difference lies in the nature of the spacer and the type of bo...
ArtikelStructure‐Property Relationships in a New Family of Photoactive Diimine‐Diphosphine Copper(I) Complexesvon Jérôme Beaudelot et al. · 09.03.2023A new family of heteroleptic diimine-diphosphine copper(I) complexes is reported, with six new complexes compared to benchmark [Cu(bcp)(DPEPhos)]PF6. These new complexes are based on 1,4,5,8-tetraazaphenanthrene (TAP) ligands with representative elec...
ArtikelIntegrating Regioselective E→ Z Isomerization of Trienones with Cascade Sequences under Photosensitizer‐Free Direct Irradiation at 390 nmvon Rajib Maity et al. · 09.03.2023The regioselective E → Z isomerization of a target olefin unit embedded in a conjugated polyene is challenging. Examples are limited only with retinal and its derivatives. The problem is further amplified when such an isomerization is integrated into...
ArtikelInsight into the Effect of Stabilizers on Anticancer and Antibacterial Activity of AgBiS2 Nanomaterialvon Anju Joseph et al. · 09.03.2023The near-infrared (NIR) light-absorbing AgBiS2 nanoparticles can be excited by single-wavelength light, which is the primary characteristic of a photoresponsive platform. Chemical synthesis of nanomaterials inevitably requires long-chain organic surf...
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