• Issue
    Volume 62, Issue 49
    December 4, 2023

Covers

Free Access

Cover Picture: Modulating Ligand-Exchange Dynamics on Metal-Organic Polyhedra for Reversible Sorting and Hybridization of Miktoarm Star Polymers (Angew. Chem. Int. Ed. 49/2023)

  • First Published: 09 October 2023
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The precise synthesis of miktoarm star polymers remains one of the great challenges in synthetic chemistry. In their Communication (e202311954), Mingxin Zhang, Panchao Yin et al. applied metal–organic polyhedra possessing logarithmic ligand exchange dynamics as templates for the feasible, reversible sorting and hybridization of miktoarm star polymers with target compositions, opening new avenues to the design of sustainable polymers.

Free Access

Inside Cover: Dithienoazepine-Based Near-Infrared Dyes: Janus-Faced Effects of a Thiophene-Fused Structure on Antiaromatic Azepines (Angew. Chem. Int. Ed. 49/2023)

  • First Published: 09 October 2023
Description unavailable

A design strategy toward near-infrared (NIR) dyes based on utilization of an antiaromatic azepine is reported by Masahito Murai, Takahiro Enoki, and Shigehiro Yamaguchi in their Research Article (e202311445). While benzo-fused azepines take bent conformations, which undergo large structural relaxation to planar conformations in the excited state, thieno-fused congeners with electron-accepting groups at both termini adopt flat conformations even in the ground state, giving rise to NIR-emissions that exceed 850 nm. Cover art: Dr. Issey Takahashi at ITbM, Nagoya University.

Free Access

Inside Back Cover: Metal-Free Electrocatalytic Diacetoxylation of Alkenes (Angew. Chem. Int. Ed. 49/2023)

  • First Published: 27 October 2023
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Electrochemical 1,2-dioxygenation is a sustainable tool for introducing important vicinal diol-related structures in alkenes. The scuba divers in the cover picture perform the highly efficient diacetoxylation of alkenes using renewable electricity as the driving force, as reported by Dirk De Vos and co-workers in their Research Article (e202311539). Excellent yields are obtained with a wide scope of aliphatic and aromatic alkenes in an atom-efficient and versatile protocol, with also application to lactone synthesis.

Free Access

Back Cover: Controlling Metal-Oxide Reducibility for Efficient C−H Bond Activation in Hydrocarbons (Angew. Chem. Int. Ed. 49/2023)

  • First Published: 20 November 2023
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The rational design of metal oxide catalysts is a challenge. In their Research Article (e202310062), Bingsen Zhang, Evgenii V. Kondratenko, Zhong-Wen Liu et al. report that structural properties of supported/bulk metal oxides can be controlled through catalyst post-treatment in an NH3⋅H2O solution because of dissolution and simultaneous precipitation of individual catalyst components. The method enables to tailor catalyst reducibility that plays a pivotal role for C−H bond activation in hydrocarbons.

Frontispiece

Free Access

Frontispiece: Visible-Light Photoswitchable Benzimidazole Azo-Arenes as β-Arrestin2-Biased Selective Cannabinoid 2 Receptor Agonists

  • First Published: 27 November 2023
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Photopharmacology. Visible-light photoswitchable benzimidazole azo- arenes as β-arrestin2-biased cannabinoid 2 receptor agonists are reported by Michael Decker et al. in their Research Article (e202306176).

Free Access

Frontispiece: Enantioselective Synthesis of Arylglycines via Pd-Catalyzed Coupling of Schöllkopf Bis-Lactim Ethers with Aryl Chlorides

  • First Published: 27 November 2023
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Amino Acid Synthesis. In their Communication (e202309868), Lukas J. Gooßen et al. report the enantioselective synthesis of arylglycines via Pd-catalyzed coupling of bis-lactim ethers with aryl chlorides.

Graphical Abstract

Free Access

Graphical Abstract: Angew. Chem. Int. Ed. 49/2023

  • First Published: 27 November 2023

Announcement

Free Access

Classifieds: Jobs and Awards, Products and Services

  • First Published: 27 November 2023
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Are you looking for a (new) job? Do you know someone who deserves an award? Are you trying to find a product or service to make your work more efficient? Our partners can help.

Team Profile

Free Access

A Team for the Development of Next-Generation Metal-Free Catalysis

  • First Published: 13 September 2023
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“The exciting aspect of this project resides in the remarkable antioxidant properties exhibited by the BCN material with low carbon content … Encouragingly, this experiment–theory–experiment model of cooperation often leads to some unexpected new discoveries…” Find out more about the collaborative work in the Xie and Lin groups.

Introducing …

Free Access

Mohammad Rafiee

  • First Published: 30 October 2023
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“The most important future application of my research is more environmentally benign chemical reactions… My favorite piece of research is the discovery of polarography by Prof. Jaroslav Heyrovský.” Find out more about Mohammad Rafiee in his Introducing… Profile.

Obituary

Free Access

Albert Eschenmoser (1925–2023): A Giant of Organic Chemistry

  • First Published: 07 November 2023
Description unavailable

Albert Eschenmoser, one of the greatest organic chemists of the past hundred years, died on July 14, 2023 at the age of 97. The extraordinary breadth of his scientific contributions ranged from synthetic methodology, structure elucidation, and synthesis of natural products to the chemical etiology of biomolecular structures.

Minireviews

Bioorthogonal Reactions

Target-Specific Bioorthogonal Reactions for Precise Biomedical Applications

  • First Published: 07 August 2023
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This minireview provides an overview of recent developments in target-specific bioorthogonal reactions and their applications for different therapeutic targets. In addition, a perspective is provided on the challenges and future directions of this emerging field for expanding their practical application.

Photocatalytic H2O2 Production

Open Access

Solar-to-H2O2 Catalyzed by Covalent Organic Frameworks

  • First Published: 13 August 2023
Description unavailable

COFs are emerging and promising candidates in photocatalytic H2O2 production. Significant progress has developed in the past several years. However, comprehensive reviews on this specific field are lacking. This minireview presents an overview of the development of COFs in photocatalytic H2O2 production, highlighting the recent strategies to optimize COF-based photocatalysts. The insights into the future development of industrial-scale and cost-effective H2O2 production are also offered.

Metal-Organic Frameworks

Open Access

Low-Valent Metals in Metal-Organic Frameworks Via Post-Synthetic Modification

  • First Published: 23 August 2023
Description unavailable

Matrix isolation of low-valent complexes within metal–organic frameworks (MOFs) facilitates exceptional gas-phase catalytic activity, stabilization of solution-inaccessible catalysts, and fundamental insight into pertinent reaction mechanisms. MOFs present an ideal porous, crystalline, and chemically mutable matrix for such species. Herein we examine synthesis techniques and applications for the matrix isolation of low-valent complexes within MOFs.

Reviews

Defluorination

Open Access

Synthetic Advantages of Defluorinative C−F Bond Functionalization

  • First Published: 22 August 2023
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This review summarizes the advantages of using C−F bonds as functional handles for chemical synthesis. Specific examples are used to illustrate how defluorofunctionalization can streamline small molecule synthesis and enable new reactions. The goal of this review is to educate chemists on the opportunities available for incorporating C−F bonds in synthetic route planning and for exploiting the unique mechanistic pathways available to C−F bonds.

Smart Textiles

Fiber Integrated Metal-Organic Frameworks as Functional Components in Smart Textiles

  • First Published: 24 August 2023
Description unavailable

The multifunctionality of metal–organic framework (MOF)-based textiles encourages innovation of a wearable platform technology capable of sensing, filtration, detoxification, and catalysis. This Review focuses on the implementation of MOFs at the fiber level to form functional components in smart textiles.

Research Articles

Photoswitches

Open Access

Visible-Light Photoswitchable Benzimidazole Azo-Arenes as β-Arrestin2-Biased Selective Cannabinoid 2 Receptor Agonists

  • First Published: 02 June 2023
Description unavailable

A new photoswitchable scaffold was developed based on the “privileged structure” of benzimidazole: 2-benzimidazole azo-arenes. This scaffold was used for the development of functionally selective cannabinoid 2 receptor (CB2R) ligands with β-arrestin2 (βarr2) bias. Compound 10 d acts as a “trans-on”-efficacy switch in βarr2-mediated endocytosis and can be used to investigate the CB2R-βarr2 endocytic pathway.

Heterogeneous Catalysis

Open Access

Controlling Metal-Oxide Reducibility for Efficient C−H Bond Activation in Hydrocarbons

  • First Published: 13 September 2023
Description unavailable

Through catalyst post-treatment in an NH3 ⋅ H2O solution, structural and chemical properties of supported metal oxide species can be controlled because of dissolution-recrystallization of amorphous or/and low-crystalline support in the parent catalyst. The method is applicable for tailoring the catalyst reducibility and thus its activity for C−H activation in hydrocarbons.

Supramolecular Chemistry | Hot Paper

Open Access

Sterically Allowed H-type Supramolecular Polymerizations

  • First Published: 05 October 2023
Description unavailable

Systematic increase in the bulkiness of dye substituents revealed an unexpected thermodynamic stability of face-to-face (H-type) stacking interactions during supramolecular polymerization. Our results contribute to the development of functional supramolecular polymers by controlling dye-dye interactions through molecular design.

Homogeneous Catalysis

Catalyst-Controlled Divergent Generations and Transformations of α-Carbonyl Cations from Alkynes

  • First Published: 19 October 2023
Description unavailable

Catalyst-controlled divergent generations of α-carbonyl cations from single alkyne functionalities and their divergent further transformations have been established. Broad spectrum of alkynes including aryl alkyne, ynamide, alkynyl ether, and alkynyl sulfide could be utilized. The intermediacy of α-carbonyl cations via the N−O bond cleavage was supported by DFT calculations in both catalytic systems.

Macrocycles

Open Access

Streamlined Protein-Protein Interface Loop Mimicry

  • First Published: 17 October 2023
Description unavailable

Backbone Matching (BM) evaluates virtual libraries of cyclic peptidomimetics containing an organic fragment, for interface loop mimicry in protein-protein interactions. It does so by comparing their backbone conformers with interface loops on the protein ligand. Hits for iNOS ⋅ SPSB2 and uPA ⋅ uPAR were validated experimentally.

Organocatalysis

Organocatalytic Dynamic Kinetic Resolution Enabled Asymmetric Synthesis of Phosphorus-Containing Chiral Helicenes

  • First Published: 16 October 2023
Description unavailable

An efficient and practical methodology has been developed for building two types of phosphorus-installing helicenes via the phosphonium salt catalyzed phospha-Michael reaction together with copper salt enabled aromatization. The scalability and practicality of this protocol were validated by the gram-scale synthesis and transformation of products, particularly towards producing novel helical phosphine ligands that were successfully utilized in metal-catalyzed reactions.

Sustainable Chemistry

Thermally Responsive Selenide-containing Materials Based on Transalkylation of Selenonium Salts

  • First Published: 18 October 2023
Description unavailable

A thermally responsive C−Se dynamic covalent chemistry (DCC) that relies on the transalkylation between selenonium salts and selenides can be easily achieved by adding alkylation reagents to the selenide compounds. By incorporating selenonium salts into polyurethane networks, we observed that the materials exhibited good healing ability at elevated temperatures as well as solvent and creep resistance at ambient temperature.

Heterogeneous Catalysis

Palladium Encapsulated by an Oxygen-Saturated TiO2 Overlayer for Low-Temperature SO2-Tolerant Catalysis during CO Oxidation

  • First Published: 17 October 2023
Description unavailable

An oxygen-saturated TiO2 overlayer was constructed on Pd nanoparticles in air at only 400 °C. The resulting catalyst with non-metal active sites exhibited an exceptional resistance to poisoning by SO2 and H2O, yielding robust CO oxidation performance under 100 ppm SO2 and 10 vol % H2O at temperatures as low as 120 °C for at least 240 h.

Catalysis

Open Access

Toward De Novo Catalyst Discovery: Fast Identification of New Catalyst Candidates for Alcohol-Mediated Morita–Baylis–Hillman Reactions

  • First Published: 13 October 2023
Description unavailable

A method to discover new catalysts: We grow a reaction network for each catalyst template (Ci) and look for catalytic activity in each reaction network. The reactant (R) reacts with the catalyst template (Ci) and forms several intermediates (Ii) before reaching a product (P) with the catalyst template regenerated.

Smiles Rearrangement

Open Access

Aryne-Enabled C−N Arylation of Anilines

  • First Published: 18 October 2023
Description unavailable

A transition metal-free C−N arylation of easily accessible tertiary anilines enabled by bifunctional arynes is described. The reaction proceeds via a tandem nucleophilic attack of anilines to arynes, followed by a Smiles-Truce rearrangement to furnish synthetically valuable and densely substituted biaryls. This protocol was further utilized for heterocyclic scaffolds, providing access to medium size azaheterocycles via n+2 carbon insertion.

Electrochemistry

Silver and Copper Nitride Cooperate for CO Electroreduction to Propanol

  • First Published: 09 October 2023
Description unavailable

Ag-doped copper nitride is a highly selective electrocatalyst for CO reduction to n-propanol leading to a record Faradaic Efficiency value of 45 % at an industrially-relevant current density of 150 mA cm−2, in an alkaline flow electrolyser.

Polycycles

Open Access

Gold-Catalyzed 1,2-Aryl Shift and Double Alkyne Benzannulation

  • First Published: 12 October 2023
Description unavailable

If the occupied position on the heterocyclic core is exceptionally electron-rich, alkyne benzannulation occurs at this position with concomitant 1,2-aryl shift. The resulting slightly curved N-doped nanographenes possess an unprecedented combination of six fused aromatic rings and strong emission of yellow light.

Fused-Ring Systems | Very Important Paper

Dithienoazepine-Based Near-Infrared Dyes: Janus-Faced Effects of a Thiophene-Fused Structure on Antiaromatic Azepines

  • First Published: 12 September 2023
Description unavailable

A seven-membered 8π azepine was employed as a key core of near-infrared (NIR) dyes. The Janus-faced effect of the thiophene-fused structure, which enhances the antiaromaticity of the azepine ring and, at the same time, relieves the antiaromaticity through the deformation from the aromatic thiophene ring to the quinoidal thienyl moiety, is effective to attain the largely red-shifted absorption and emission in the NIR region.

Na-ion Batteries

Open Access

Synergetic Coupling of Redox-Active Sites on Organic Electrode Material for Robust and High-Performance Sodium-Ion Storage

  • First Published: 14 September 2023
Description unavailable

Hexanol hexaazatrinaphthalene, an organic electrode material with synergetic coupling effects of abundant redox-active sites and stable conjugated cores, via nine-electron transfer mechanism, delivers excellent rate capability, and robust cycling performance in sodium-ion batteries.

Electrocatalysis

Metal-Free Electrocatalytic Diacetoxylation of Alkenes

  • First Published: 19 September 2023
Description unavailable

A highly efficient electrocatalytic 1,2-dioxygenation of alkenes utilizing readily available materials in ambient conditions is developed. The protocol is widely applicable to aliphatic and aromatic alkenes with excellent faradaic efficiencies and yields of up to 96 %. The versatility of the method is expanded with alkenoic acids towards lactone derivatives and with other carboxylic acids like HCOOH.

Black Phosphorus | Hot Paper

Reaction Chemistry at Discrete Organometallic Fragments on Black Phosphorus

  • First Published: 16 October 2023
Description unavailable

Molecular functionalization techniques are leveraged to anchor well-defined organometallic fragments on the surface of black phosphorus. The functionalized nanosheets feature a high density of metal sites, with discrete and robust M−P bonds that are stable to subsequent transformations. The Tolman electronic parameter and steric bulk of bP are also estimated relative to molecular phosphines.

Polymer Recycling | Very Important Paper

Polymer Multi-Block and Multi-Block+ Strategies for the Upcycling of Mixed Polyolefins and Other Plastics

  • First Published: 18 October 2023
Description unavailable

A series of multi-block copolymers with tunable microstructures were prepared and used as compatibilizer additives for upcycling mixtures of polyolefins with other plastics. Furthermore, a multi-block+ strategy based on a reactive telechelic block copolymer platform was demonstrated to enable block extension during in situ melt blending of mixed plastics, leading to better compatibilizing properties and 3D printing capability.

Fluorescent Probes | Hot Paper

An Extended NIR-II Superior Imaging Window from 1500 to 1900 nm for High-Resolution In Vivo Multiplexed Imaging Based on Lanthanide Nanocrystals

  • First Published: 20 October 2023
Description unavailable

We developed a series of novel lanthanide-doped nanoparticles in the whole near-infrared region (NIR) beyond 1700 nm. Inspired by the scattering and water absorption, we then defined the NIR-II long-wavelength (NIR-II-L, 1500 nm–1900 nm) window for high-resolution multiplexed imaging of lymph, blood vessels and intestines.

Zeolites

Constructing Intrapenetrated Hierarchical Zeolites with Highly Complete Framework via Protozeolite Seeding

  • First Published: 11 October 2023
Description unavailable

A single-crystalline intrapenetrated hierarchical zeolite with highly complete framework was synthesized via protozeolite seeding. The protozeolite provided abundant nucleation sites for surrounding precursors to be crystallized, followed by oriented coalescence of crystallites resulting in the formation of intrapenetrated mesopores. The as-prepared zeolite presented excellent performance in the methanol-to-propylene reaction.

Hybrid Aqueous Batteries

High-Energy Aqueous/Organic Hybrid Batteries Enabled by Cu2+ Redox Charge Carriers

  • First Published: 18 October 2023
Description unavailable

High-energy Li||S hybrid batteries were designed via matching S cathodes in aqueous Cu2+ ion-based electrolyte and Li anodes in organic electrolyte. The Li||S hybrid batteries deliver a high discharge voltage and satisfactory capacity, contributing to incredible energy density.

Nanographenes

Open Access

Tetrahedraphene: A Csp3-centered 3D Molecular Nanographene Showing Aggregation-Induced Emission

  • First Published: 17 October 2023
Description unavailable

Supramolecular interactions in the solid state (X-ray) and solution (mixtures of THF/H2O) control the photophysical properties! A singular 3D nanographene (Tetrahedraphene) shows a remarkable aggregation-induced emission upon water addition changing from blue in solution to vivid yellow colour in the precipitated solid. TDDFT calculations predict the formation of efficient π–π interactions in solution, thus supporting the photophysical findings.

Biosensors

Hierarchical Fluid Interface Enables Spatiotemporal Regulation of Ligand Distribution to Increase Kinetics and Thermodynamics of Interfacial Binding Reaction

  • First Published: 18 October 2023
Description unavailable

A hierarchical fluid interface (HieFluidFace) based on aptamer-functionalized Au nanoparticles (“islands”) and fluid fluorescent aptamer ligands (“rafts”) was engineered on a microfluidic chip surface. HieFluidFace allowed to increase the rate and thermodynamic favorability of interfacial binding reactions via spatiotemporal regulation of ligand distribution, and was used for efficient capture and direct identification of circulating tumor cells from clinical samples.

Immunotherapy

Synthetic High-Density Lipoprotein-Based Nanomedicine to Silence SOCS1 in Tumor Microenvironment and Trigger Antitumor Immunity against Glioma

  • First Published: 17 October 2023
Description unavailable

A nanomedicine was designed to modulate the tumor microenvironment (TME) against glioma (GBM). Upon intravenous injection, the nanomedicine penetrated the blood–brain barrier and accumulated within the TME of GBM-bearing mice, which subsequently abolished the negative feedback regulation function of SOCS1 on dendritic cell maturation and T cell proliferation, elicited strong cytotoxic T lymphocyte responses, and inhibited tumor growth.

Covalent Organic Frameworks

Highly Flexible Dielectric Films from Solution Processable Covalent Organic Frameworks

  • First Published: 18 October 2023
Description unavailable

Porous polymers, like covalent organic frameworks, are promising materials for a wide variety of applications. However, unlike conventional polymers, they are challenging to mold, shape, or process. Here we show how insoluble COFs, functionalized with oligoether sidechains, can be solution cast into high-dielectric films, with excellent flexibility and mechanical strength.

K-ion Batteries

Green Ether Electrolytes for Sustainable High-voltage Potassium Ion Batteries

  • First Published: 17 October 2023
Description unavailable

A green ether solvent is reported through a rational design of carbon chain regulation that tunes steric hindrance for an efficient solvation structure. Such a structure significantly reduces the solvent‘s biotoxicity, and the tuned solvation structure results in sustainable high-voltage electrolytes for alkali metal-ion batteries.

Solar Cells

Optimized Crystal Framework by Asymmetric Core Isomerization in Selenium-Substituted Acceptor for Efficient Binary Organic Solar Cells

  • First Published: 12 October 2023
Description unavailable

The synergistic strategies of the regional selenium isomerization and asymmetric crystal engineering are applied to synthesize isomeric small molecular acceptors. Benefiting from optimized crystal packing, favourable morphology and ordered molecular arrangement, A-OSeF-based binary organic solar cells yield a champion efficiency of 18.5 % and low energy loss among selenium-containing acceptors.

Photocatalysis

Photosynthesis of Benzonitriles on BiOBr Nanosheets Promoted by Vacancy Associates

  • First Published: 11 October 2023
Description unavailable

BiOBr photocatalysts with different surface vacancy associates were successfully synthesized. Vacancy associates of Br−Bi−Br triple atom vacancy (VBrBiBr) and oxygen vacancies can generate benzonitrile with high selectivity in the photocatalytic ammoxidation of benzyl alcohol by providing adsorption activation sites for NH3 and O2 and reaction sites for the multi-step formation of imine intermediates and oxidation to benzonitrile.

Electrocatalytic CO2 Reduction

Enhancing Local CO2 Adsorption by L-histidine Incorporation for Selective Formate Production Over the Wide Potential Window

  • First Published: 19 October 2023
Description unavailable

An effective approach towards enhancing the CO2 adsorption capacity of Bi-based catalysts was demonstrated via the L-histidine incorporation. The improved CO2 chemical adsorption and electron-rich nature of resultant catalysts enables high Faradaic efficiency for formate production in an ultra-wide potential window even with low-concentration CO2 feeding. (TETA and DEA refer to triethylenetetramine and diethanolamine, respectively).

Photocatalysis | Hot Paper

Criteria for Efficient Photocatalytic Water Splitting Revealed by Studying Carrier Dynamics in a Model Al-doped SrTiO3 Photocatalyst

  • First Published: 19 October 2023
Description unavailable

Photoluminescence study of a model Al-doped SrTiO3 photocatalyst reveals that by suppressing photocarrier recombination and establishing a facile charge separation and extraction mechanism, a quantum efficiency of almost 100 % can be achieved even with a very short (sub-ns) intrinsic photocarrier lifetime, challenging the belief that a long carrier lifetime is a fundamental requirement.

Bismuth Chemistry

Open Access

Mechanistic Studies on the Bismuth-Catalyzed Transfer Hydrogenation of Azoarenes

  • First Published: 28 September 2023
Description unavailable

We report a combined experimental and computational study of the bismuth-catalyzed transfer hydrogenation of azoarenes. With the protocol using p-trifluoromethylphenol and pinacolborane, we identified the role of protic and hydridic hydrogens through kinetic analysis and reactivity studies. The possibility of Bi-ligand cooperativity was assessed through isotope labeling experiments. This work validates the notion of Bi(I)/Bi(III) redox cycling.

Supramolecular Chemistry | Very Important Paper

Open Access

Kinetic Delay in Cooperative Supramolecular Polymerization by Redefining the Trade-Off Relationship between H-Bonds and Van der Waals/π–π Stacking Interactions

  • First Published: 23 October 2023
Description unavailable

Proper molecular engineering can open new opportunities to create kinetically metastable states in monomers undergoing cooperative supramolecular polymerizations. This occurs by favoring dispersive interactions over H-bonds and thereby rebalancing the interplay between π–π stacking, Van der Waals, and hydrogen-bonding interactions.

Enzyme Catalysis

A Mushroom P450-Monooxygenase Enables Regio- and Stereoselective Biocatalytic Synthesis of Epoxycyclohexenones

  • First Published: 18 October 2023
Description unavailable

PanH, a cytochrome P450 monooxygenase, was identified and verified as the enzyme responsible for epoxycyclohexenone formation in panepoxydone biosynthesis in the basidiomycete mushroom Panus rudis. A PanH-producing yeast as a biocatalyst enabled an enzymatic approach to synthesize a library of bioactive epoxycyclohexenone compounds.

Supramolecular Chemistry | Hot Paper

Open Access

Stabilization of Guest Molecules inside Cation-Lidded Cucurbiturils Reveals that Hydration of Receptor Sites Can Impede Binding

  • First Published: 09 October 2023
Description unavailable

Alkali metal ions docked to water-soluble macrocyclic receptors can unexpectedly enhance the binding of guest molecules. For instance, with cucurbit[5]uril and large cations, methane and ethane binding increased 5–8 times due to water molecule removal during cation binding. This reveals a previously unnoticed steric hindrance of solvation water molecules near receptor binding sites.

Electrocatalysis | Very Important Paper

Unveiling the Electrolyte Cations Dependent Kinetics on CoOOH-Catalyzed Oxygen Evolution Reaction

  • First Published: 21 October 2023
Description unavailable

The electrolyte cations dependent kinetics on CoOOH catalyzed oxygen evolution reaction (OER) is derived from cation intercalation, which can rationally tailor the formation energy of high-valent OER-active *O−Co(IV) species during OER process. This finding provides an informative picture to understand the complicated mechanism of electrolyte cation-targeted electrocatalysis.

Water Splitting | Hot Paper

Reducing the Ir−O Coordination Number in Anodic Catalysts based on IrOx Nanoparticles towards Enhanced Proton-exchange-membrane Water Electrolysis

  • First Published: 22 October 2023
Description unavailable

Reducing the coordination number is feasible to lower the rate-determination-step energy barrier, thus accelerating the electrocatalytic reaction process. Our designed low-coordination IrOx delivers superior activity as well as excellent stability in water electrolyzers.

Single-Atom Catalysts

Construction of Low-Coordination Cu−C2 Single-Atoms Electrocatalyst Facilitating the Efficient Electrochemical CO2 Reduction to Methane

  • First Published: 24 October 2023
Description unavailable

Utilizing the special structure of 1,3,5-triynylbenzene, Cu single atom catalysts with a Cu−C2 coordination structure were prepared for the first time and showed excellent performance in the electrochemical reduction of CO2 (e-CO2RR) process. Comprehensive experiments and calculations confirmed that the Cu−C2 structure not only endowed the Cu single atoms center with more positive charge, but also promoted the formation of H⋅, which improved the electrocatalytic performance of CO2RR to CH4.

Electrocatalytic O2 Reduction

Modulating Coordination of Iron Atom Clusters on N,P,S Triply-Doped Hollow Carbon Support towards Enhanced Electrocatalytic Oxygen Reduction

  • First Published: 23 October 2023
Description unavailable

A general diffusion-controlled strategy is proposed to synthesize metal atom-clusters with engineered coordination in N,P,S triply-doped hollow carbon. The optimum FeACs/NPS−HC shows remarkably enhanced catalytic activity for oxygen reduction, compared with the benchmark analogue of N-coordinated iron single-atoms in N-doped carbon (FeSAs/N−C). This work presents a paradigm for the regulation and optimization of atomically dispersed catalysts.

Photoaffinity Labeling

Open Access

Fluorogenic Photo-Crosslinking of Glycan-Binding Protein Recognition Using a Fluorinated Azido-Coumarin Fucoside

  • First Published: 17 October 2023
Description unavailable

Photoaffinity labeling has been a staple of chemical biology for the capture of non-covalent interactions. Through conjugation of a trifluorinated 7-azido-coumarin to an α-fucoside, we demonstrate fluorogenic photo-crosslinking of glycan-protein interactions. This strategy and these “fluoro-crosslinkers” enable traceable photoaffinity labeling and could prove uniquely valuable for imaging biological recognition of glycans.

Porous Materials | Hot Paper

Supracluster Assembly of Archimedean Cages with 72 Hydrogen Bonds for the Aldol Addition Reaction

  • First Published: 25 October 2023
Description unavailable

Al−O clusters-based supraclusters presenting multiple hydrogen-bonded porous assemblies can offer outstanding catalysis ability both in the homogeneous and heterogeneous phases. The supracluster proposed here will build a bridge between “supramolecule” and “supraparticle”, and provide new perspectives for synthesizing zeolite-like materials.

Photoluminescence

Open Access

pH-Responsive Near-Infrared Emitting Gold Nanoclusters

  • First Published: 19 October 2023
Description unavailable

Near-infrared emitting gold nanoclusters with reversible pH responsiveness have been developed by the incorporation of tertiary amine groups in the surface ligands. The amine groups change the highest occupied molecular orbital upon their pH-induced protonation and deprotonation, resulting in photoluminescence quenching.

Gold Catalysis

Open Access

Chiral Auxiliary Approach for Gold(I)-Catalyzed Cyclizations

  • First Published: 23 October 2023
Description unavailable

The stereoselective gold(I)-catalyzed cascade cyclization of 1,5-enynes and alkoxycyclization of 1,6-enynes with chiral auxiliaries has been developed, affording, after hydrolysis, synthetically challenging enantioenriched ketones. This chiral auxiliary approach is an alternative to the use of complex chiral catalysts in gold(I)-catalyzed asymmetric cyclizations.

Photocatalysis

UV-to-NIR Harvesting Conjugated Porous Polymer Nanocomposite: Upconversion and Plasmon Expedited Thioether Photooxidation

  • First Published: 12 October 2023
Description unavailable

Surface-functionalized upconversion nanoparticles are covalently linked to conjugated porous organic polymers, followed by the loading of gold nanoparticles to form a UV-to-NIR absorbing photocatalyst, UC−POP−Au. The synergistic influence of plasmon absorption and upconversion luminescence improves photocatalytic oxidation of thioethers, including the detoxification of chemical warfare agents under natural sunlight and solvent-free conditions.

Aqueous Batteries

Six-Electron-Redox Iodine Electrodes for High-Energy Aqueous Batteries

  • First Published: 20 October 2023
Description unavailable

Six-electron redox chemistry of I2 electrodes is achieved via the synergistic effect of redox-ion charge-carriers and halide ions in aqueous electrolytes. The unique energy storage mechanism leads to high capacity and potential of I2 electrodes, contributing to enhanced energy density of corresponding aqueous batteries.

Photocatalysis

Metal-Free Photocatalytic CO2 Reduction to CH4 and H2O2 under Non-sacrificial Ambient Conditions

  • First Published: 18 October 2023
Description unavailable

A metal-free photocatalyst achieves high electronic selectivity for CH4 and facile separation of H2O2 in non-sacrificial ambient conditions with only CO2 and H2O. This exceptional performance is attributed to a long-lived oxygen-centered radical in the excited electron acceptor, promoting the formation of a stabilized five-member-ring cyclic intermediate with lower energy, leading to an 90 % selectivity for the eight-electron product CH4.

Hydrogen-Bonded Organic Frameworks

Hydrogen-Bonding Assembly Meets Anion Coordination Chemistry: Framework Shaping and Polarity Tuning for Xenon/Krypton Separation

  • First Published: 25 October 2023
Description unavailable

The marriage between hydrogen bonding and the coordination chemistry of halide anions offers a promising strategy to construct crystalline microporous frameworks with adaptive cavities and fine-tunable surface polarity for efficient Xe/Kr separation. The activated frameworks show preferential binding towards Xe because of the enhanced polarizability and the pore confinement effect.

Acidic O2 Evolution

Co−Co Dinuclear Active Sites Dispersed on Zirconium-doped Heterostructured Co9S8/Co3O4 for High-current-density and Durable Acidic Oxygen Evolution

  • First Published: 19 October 2023
Description unavailable

Our study makes a stride in the discovery of acid-stable Co−Co dinuclear active sites (DASs) for PEM through single-atom tuning strategy. The XAFS elucidated the incorporation of Zr greatly facilitated the generation of Co−Co DASs layer with stretching of cobalt oxygen bond and S−Co−O heterogeneous grain boundaries interfaces (HGBIs), engineering attractive activity of ultra-low overpotential and 500 h superior durability in acid.

Supramolecular Chemistry

Cascade Energy Transfer and White-Light Emission in Chirality-Controlled Crystallization-Driven Two-Dimensional Co-assemblies from Donor and Acceptor Dye-Conjugated Polylactides

  • First Published: 16 October 2023
Description unavailable

White-light emission by sequential Förster resonance energy transfer from thermally robust precision two-dimensional (2D) assemblies is unravelled. It is driven by stereocomplex crystallization between two complementary chromophore-conjugated polylactide stereoisomers in the presence of an external dye.

Cage Structures

Open Access

A Lantern-Shaped Pd(II) Cage Constructed from Four Different Low-Symmetry Ligands with Positional and Orientational Control: An Ancillary Pairings Approach

  • First Published: 10 October 2023
Description unavailable

A Pd(II) lantern-shaped cage with four different low-symmetry ligands, with positional and orientational control, has been built by using ancillary pairings. In this approach, the ligands with Pd(II)-binding sites come together in complementary ways due to their denticity (3 : 1 or 2 : 2) and/or hydrogen-bonding capability (AA : DD or AD : DA).

Peptides | Very Important Paper

Artificial Peptide-Protein Necrosomes Promote Cell Death

  • First Published: 23 October 2023
Description unavailable

Inspired by the structural feature of natural necrosome, kinase-biomimetic D-retro-inverso peptides (DRI-peptides) are designed and able to strongly associate with kinases. This feature of the peptides facilitates formation of artificial peptide-protein necrosomes and thus selectively activating the necrotic signaling pathway to induce cellular necroptosis.

Epigenetics

Open Access

Substrates and Cyclic Peptide Inhibitors of the Oligonucleotide-Activated Sirtuin 7

  • First Published: 24 October 2023
Description unavailable

Broad screening of the substrate specificity of SIRT7 revealed a strong preference for the cleavage of long-chain acyllysine modifications. The activity was substantially increased in the presence of oligonucleotides or nucleosome particles. Finally, random nonstandard peptide integrated discovery (RaPID) delivered a cyclopeptide with potency in the sub-micromolar range and selectivity for SIRT7, which binds and stabilizes SIRT7 in cells.

Diradicaloids

Rational Design of an Air-Stable, High-Spin Diradical with Diazapyrene

  • First Published: 18 October 2023
Description unavailable

A general method has been developed for installing stable polyradicals into polycyclic π-systems, as illustrated by the formation of an air-stable, high-spin carbon-based diradical with a new ferromagnetic coupling motif of diazapyrene. The structure of the diradical was confirmed by X-ray diffraction, while the magnetic measurements provided unambiguous evidence for the high-spin ground state and a long spin relaxation process.

Heterocycles

Open Access

The Construction of Highly Substituted Piperidines via Dearomative Functionalization Reaction

  • First Published: 20 October 2023
Description unavailable

The stepwise dearomative functionalization reaction of pyridines generates highly substituted piperidines, featuring diverse functional handles, with excellent site-, regio-, and diastereoselectivity. The origin of the unprecedented selectivities and additional insights into the reaction mechanism are discussed based on combined experimental mechanistic studies and density functional theory computations.

H2O2 Electrosynthesis

Lattice Distortion and H-passivation in Pure Carbon Electrocatalysts for Efficient and Stable Two-electron Oxygen Reduction to H2O2

  • First Published: 23 October 2023
Description unavailable

This study provides a new understanding on the activation of 2e oxygen reduction reaction (ORR) of carbon materials, through H-passivated and distorted lattices, and demonstrated how carbon cloth can be offered via this strategy with excellent and stable 2e ORR for the H2O2 production.

Helical Polymers

Single-Crystal-to-Single-Crystal Topochemical Synthesis of a Collagen-inspired Covalent Helical Polymer

  • First Published: 20 October 2023
Description unavailable

Synthetic covalent helical polymers in solid form are in high demand. By biomimicry, we designed a dipeptide monomer containing azide and alkyne that organize in head-to-tail as supramolecular helices in their crystals. Upon heating, the monomer undergoes SCSC TAAC polymerization to yield a covalent helical polymer. Single crystals of this fully organic polymer show high flexural strength, compressive strength and load-bearing capacity.

MOF Membranes | Hot Paper

Modular Customization and Regulation of Metal–Organic Frameworks for Efficient Membrane Separations

  • First Published: 16 October 2023
Description unavailable

A modular customization strategy was applied for efficient MOF membrane fabrication. MOF material screening, defect-free membrane output, membrane physicochemical property regulation and separation applications can be rapidly realized by separately designing and modifying the MOF module within the membrane. High separation performance is easily achieved, which can meet diverse separation requirements.

Communications

Asymmetric Synthesis

Open Access

Enantioselective Synthesis of Arylglycines via Pd-Catalyzed Coupling of Schöllkopf Bis-Lactim Ethers with Aryl Chlorides

  • First Published: 06 September 2023
Description unavailable

Catalytic methylnaphthyl(XPhos)-palladium bromide promotes the coupling of chiral tert-leucine-derived Schöllkopf bis-lactim ether with cheap aryl chlorides at room temperature in yields up to 95 % and >25 : 1 dr. This enables a convenient access to non-natural tertiary arylglycines, which are key structural motifs in several top-selling drugs. This protocol is also suitable for the late-stage functionalization of common pharmaceuticals.

Polymers

Modulating Ligand-Exchange Dynamics on Metal-Organic Polyhedra for Reversible Sorting and Hybridization of Miktoarm Star Polymers

  • First Published: 04 September 2023
Description unavailable

Metal-organic polyhedra possess logarithmic ligand-exchange dynamics that can only be activated at high temperatures. They have been applied as crosslinker templates for the synthesis of miktoarm star polymers with target compositions by thermal annealing of the mixture of star homo-polymers. The reversible sorting process can be conducted through a typical solvent extraction procedure.

Photoredox Catalysis

Open Access

Synthesis of α-Branched Enones via Chloroacylation of Terminal Alkenes

  • First Published: 03 October 2023
Description unavailable

We show the conversion of unactivated alkenes into α-branched α,β-unsaturated ketones (enones) and esters. Regioselective chloroacylation with acyl chlorides and chloroformates takes place under cooperative nickel/photoredox catalysis. Subsequent HCl elimination provides enones and α,β-unsaturated esters that are not accessible via the conventional acylation approaches that provide the other, linear constitutional isomer.

Soft Matter | Hot Paper

Uniform Colloidal Polymer Rods by Stabilizer-Assisted Liquid-Crystallization-Driven Self-Assembly

  • First Published: 14 October 2023
Description unavailable

Uniform colloidal polymer rods/disks with tunable aspect ratios and well-defined internal molecular packing and orientations were successfully achieved from homopolymers or random copolymers by stabilizer-assisted liquid-crystallization-driven self-assembly. They show an unusual photo-induced fluorescence enhancement and accompanying memory effect, which have been used for high-level encryption and secure delivery of paper documents.

OLEDs

Regulation of Multiple Resonance Delayed Fluorescence via Through-Space Charge Transfer Excited State towards High-Efficiency and Stable Narrowband Electroluminescence

  • First Published: 18 October 2023
Description unavailable

The dual steric and electronic effects of through-space charge transfer excited states have been exploited to concurrently shorten the delayed fluorescence lifetime and mitigate the aggregation-caused emission quenching of multiple resonance B−N emitter. Organic light-emitting diodes based on the new emitter show high efficiencies, small efficiency roll-offs, and good operational stability.

Polymerization | Hot Paper

Open Access

Toughening Brittle Bio-P3HB with Synthetic P3HB of Engineered Stereomicrostructures

  • First Published: 25 October 2023
Description unavailable

The longstanding mechanical brittleness issue associated with stereoperfect biological or synthetic P3HB is solved through blending it with synthetic P3HB with specifically engineered stereomicrostructures, which not only drastically enhances the toughness by >156× and optical clarity but also largely maintains its otherwise desirably high elastic modulus, tensile strength, melting temperature.

Radical Reactions

Electron-Transfer Protocol for the Hydroxyalkenylation of Alkenes Using 1,2-Bis(phenylsulfonyl)ethylene

  • First Published: 18 October 2023
Description unavailable

A simple protocol for alkene hydroxyalkenylation by 1,2-bis(phenylsulfonyl)ethylene was developed using persulfate anion as a one-electron oxidizing reagent. Regioselective hydroxyalkenylation was observed for a variety of substituted alkenes. A photocatalytic protocol for alkoxyalkenylation using an acridinium salt was also successful.

Electrosynthesis

Substrate-Mediator Duality of 1,4-Dicyanobenzene in Electrochemical C(sp2)−C(sp3) Bond Formation with Alkyl Bromides

  • First Published: 19 October 2023
Description unavailable

1,4-Dicyanobenzene acts as a substrate and a mediator in an electrochemical C(sp2)−C(sp3) bond-forming reaction with alkyl bromides. The reaction conditions avoid competing alkyl radical homocoupling and allows for the accommodation of alkyl bromides with oxidatively sensitive and acidic functional groups that are difficult to incorporate using alternative C(sp3) precursors.

Synthetic Methods

Open Access

Ligand-Enabled Double γ-C(sp3)−H Functionalization of Aliphatic Acids: One-Step Synthesis of γ-Arylated γ-Lactones

  • First Published: 18 October 2023
Description unavailable

A Pd(II)-catalyzed tandem γ-methylene C−H arylation and lactonization of aliphatic acids was enabled by a L,X-type CarboxPyridone ligand. A wide range of γ-arylated -γ-lactones are synthesized in a single step from aliphatic acids in moderate to good yield. Arylated lactones can readily be converted into disubstituted tetrahydrofurans, a prominent scaffold amongst bioactive molecules.

Polyoxometalates | Very Important Paper

Open Access

Clustering Six Electrons within “Dawson-Like” Polyoxometalate: An Open Route toward Its Post-functionalization

  • First Published: 13 October 2023
Description unavailable

The super-reduction of Dawson-like polyoxometalate (POM) [H2AsW18O60]7− in water involves a disproportionation process generating POM with a metal-metal bonded triad as evidenced by single crystal X-ray diffraction and multi-nuclear magnetic resonance investigations. Then, the resulting six-electron reduced POM was used as a precursor to construct the largest POM containing W4+ reported to date.

Carbenes

Light-Driven Enantioselective Carbene-Catalyzed Radical-Radical Coupling

  • First Published: 16 October 2023
Description unavailable

An enantioselective radical-radical coupling using combined photoredox/N-heterocyclic carbene (NHC) catalysis was developed. The coupling of a ketyl radical and an sp3-carbon radical allows access to α-chiral ketones in moderate-to-good yields and enantioselectivities. Computational investigations reveal the N-heterocyclic carbene controls the double-facial selectivity of the ketyl radical and the alkyl radicals, respectively.

Small-Ring Compounds | Hot Paper

Open Access

Divergent Synthesis of 1,2,3,4-Tetrasubstituted Cyclobutenes from a Common Scaffold: Enantioselective Desymmetrization by Dual-Catalyzed Photoredox Cross-Coupling

  • First Published: 18 October 2023
Description unavailable

The metallaphotoredox-enabled enantioselective desymmetrization of a novel dibromocyclobutene facilitates access to a versatile cyclobutene intermediate that can be functionalized to access a wide range of chiral 1,2,3,4-tetrasubstituted cyclobutenes and cyclobutanes.

Corannulenes

Mixed-Valence BN-Doped Corannulene Trimer Radical Cations

  • First Published: 17 October 2023
Description unavailable

The structure and properties of the radical cations of mixed-valence polycyclic aromatic hydrocarbon trimers have remained elusive because of their intrinsic instability. This has been overcome by the reaction of BN-doped corannulenes with oxidants. EPR spectroscopic analysis of the resulting compounds demonstrated the existence of two unpaired electrons, and theoretical calculations confirmed the uneven distribution of spin density.

Organic Electronics | Very Important Paper

Propeller vs Quasi-Planar 6-Cantilever Small Molecular Platforms with Extremely Two-Dimensional Conjugated Extension

  • First Published: 19 October 2023
Description unavailable

Two exotic 6-cantilever small molecular platforms, characteristic of quite different molecular configurations of propeller and quasi-plane, are established by extremely two-dimensional conjugated extension on different elementary units (triptycene vs. triphenylene), demonstrating two pioneered yet highly promising molecular innovation platforms for organic semiconductors.

Asymmetric Catalysis

Copper-Catalyzed Asymmetric Arylation of α-Substituted Cyanoacetates Enabled by Chiral Amide Ligands

  • First Published: 23 October 2023
Description unavailable

Asymmetric synthesis of α-(heteroaryl)-α-alkyl cyanoacetates was achieved by Cu-catalyzed arylation of α-alkyl substituted cyanoacetates under the assistance of two types of chiral ligands, (S)-nobin-embodied picolinamides and L-hydroxyproline-derived amides. The reaction afforded the coupling products bearing an all-carbon quaternary center tethered with convertible functional groups in good to excellent enantioselectivities (up to 95 % ee).

Organic Photodetectors

Enhanced Gain in Organic Photodetectors Using the Polymer with Singlet Open-Shell Ground State

  • First Published: 16 October 2023
Description unavailable

To address the challenge of achieving high photoresponse and low dark or noise current with a fast response speed under a low bias in polymer photodetectors, this study demonstrates the potential of incorporating the polymer with singlet open-shell ground state in the active layer to enhance the performance of organic photodetectors.

High-Spin Metal Clusters | Hot Paper

High-Spin and Reactive Fe13 Cluster with Exposed Metal Sites

  • First Published: 23 October 2023
Description unavailable

A high nuclearity Fe13 cluster with metal-metal interactions was prepared from a WFe3S3 precursor. This compound displays a large room temperature spin value and undergoes core structural rearrangement upon multielectron group transfer chemistry.

Analytical Chemistry

Coding Intrinsic Disorder into DNA Hybridization Probes Enables Discrimination of Single Nucleotide Variants over Wide and Tunable Temperature Ranges

  • First Published: 18 October 2023
Description unavailable

Classic hybridization probes for discriminating single nucleotide mutations typically work at elevated temperatures and in very narrow temperature intervals (ΔT) due to the high entropy penalty. By adding intrinsic disorder into hybridization probes, we successfully expanded ΔT from less than 10 °C to over 30 °C.

3D COFs | Hot Paper

Multicomponent Synthesis of Imidazole-Linked Fully Conjugated 3D Covalent Organic Framework for Efficient Electrochemical Hydrogen Peroxide Production

  • First Published: 25 October 2023
Description unavailable

A robust imidazole-linked fully conjugated 3D covalent organic framework was synthesized via the one-pot Debus-Radziszewski multicomponent reaction. The material showed excellent two electron oxygen-reduction activity and when it was used as cathode catalyst and assembled into the electrolyzer, the devices showed high electrochemical production rate of H2O2 up to 326.9 mmol g−1 h−1.

Homogeneous Catalysis

Intermolecular Carbophosphination of Alkynes with Phosphole Oxides via Ni−Al Bimetal-Catalyzed C−P Bond Activation

  • First Published: 17 October 2023
Description unavailable

The intermolecular carbophosphination reaction of alkynes or alkenes with unreactive C−P bonds remains an elusive challenge. Herein, we used a Ni−Al bimetallic catalyst to realize an intermolecular carbophosphination reaction of alkynes with 5-membered phosphole oxides, providing a series of 7-membered phosphepines in up to 94 % yield.

Silicon Chemistry

Open Access

Geometrically Compelled Silicon(II)/Silicon(IV) Donor–Acceptor Interaction Enables the Enamination of Nitriles

  • First Published: 25 October 2023
Description unavailable

Hydrido-benzosiloles bearing a side arm of the silylenyl group are prepared, all featuring the unique silicon(II)→silicon(IV) donor-acceptor interaction that facilitates the enamination of α-H-bearing nitriles to afford the edge-fused Si-heterotricycles.