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Cover Picture: Tetrazole Diversification of Amino Acids and Peptides via Silver-Catalyzed Intermolecular Cycloaddition with Aryldiazonium Salts (Angew. Chem. Int. Ed. 37/2023)
- First Published: 24 August 2023

A general tetrazole diversification platform of amino acids is presented by Ilan Marek, Fa-Guang Zhang, Jun-An Ma, and co-workers in their Research Article (e202304740). This method transformed proteinogenic α-amino acids into a plethora of tetrazole-decorated amino acid derivatives via silver-catalyzed intermolecular cycloaddition with aryldiazonium salts. The background of the cover image shows the key tetrazole structure surrounded by selected amino acid-derived tetrazoles and some starting amino acids.
Inside Cover: Extremely Electron-Withdrawing Lewis-Paired CN Groups for Organic p-Dopants (Angew. Chem. Int. Ed. 37/2023)
- First Published: 09 August 2023

Molecular doping is a key technique to modulate optical, electrical, and electronic properties of organic semiconductors. However, typical functional groups in organic p-dopants have insufficient electron-withdrawing strength, and inevitable dopant diffusion in host matrices degrades doping stabilities. In their Research Article (e202304245), Jaeyoung Jang and co-workers develop extremely electron-withdrawing Lewis-paired CN groups as a new class of building blocks for designing strong organic p-dopants with excellent doping stability.
Inside Back Cover: Asymmetric (4+n) Cycloadditions of Indolyldimethanols for the Synthesis of Enantioenriched Indole-Fused Rings (Angew. Chem. Int. Ed. 37/2023)
- First Published: 26 July 2023

Developing indolyldimethanols as four-carbon platform molecules for enantioselective cycloadditions is like climbing a higher peak of the mountain: full of challenges but exciting. In their Research Article (e202305450), Shao-Fei Ni, Wei Tan, Feng Shi et al. describe catalytic asymmetric (4+n) cycloadditions of indolyldimethanols, leading to the construction of enantioenriched indole-fused rings.
Back Cover: Elongated Bacterial Pili as a Versatile Alignment Medium for NMR Spectroscopy (Angew. Chem. Int. Ed. 37/2023)
- First Published: 14 July 2023

A liquid-crystalline alignment medium for recording residual dipolar couplings (RDCs) by NMR spectroscopy is reported by Loïc Salmon, Christoph Giese and co-workers in their Research Article (e202305120). The medium relies on filamentous type 1 pili from E. coli, is compatible with harsh experimental conditions and allows RDC measurements for proteins, nucleic acids and small organic molecules.
Frontispiece
Frontispiece: Facile Synthesis of Linear and Cyclic Poly(diphenylacetylene)s by Molybdenum and Tungsten Catalysis
- First Published: 06 September 2023

Polymerization. In their Research Article (e202302332), Tsuyoshi Taniguchi, Katsuhiro Maeda et al. report two improved methods for the synthesis of functionalized poly(diphenylacetylene)s.
Frontispiece: A Broad Light-Harvesting Conjugated Oligoelectrolyte Enables Photocatalytic Nitrogen Fixation in a Bacterial Biohybrid
- First Published: 06 September 2023

Nitrogen Fixation. In their Communication (e202307101), Guillermo C. Bazan et al. developed a new strategy to enable light-driven nitrogen fixation in non-photosynthetic bacteria by integrating the novel conjugated oligoelectrolyte into Azotobacter vinelandii.
Graphical Abstract
Graphical Abstract: Angew. Chem. Int. Ed. 37/2023
- First Published: 06 September 2023
Introducing …
A. J. Andre Cobb
- First Published: 10 July 2023

“A turning point in my career was my former colleague at Reading, Joe Sweeney, mentioning Sam Gellman (UW-Madison) to me, which led to me spending a month there on a Royal Society Travel Grant, and becoming obsessed with foldamers … The most important qualities of a mentor are to listen, not have any preconceived thoughts and admit when you don't know something.” Find out more about A. J. Andre Cobb in his Introducing … Profile.
Sona Krajcovicova
- First Published: 27 July 2023

“A key experience in my education and career was when I faced rejection and failure because it built up my resilience. Even when it hurt, it taught me a lot about myself … In five years, I hope to be happy, healthy, (still) sane, and hopefully also an independent young Professor …” Find out more about Sona Krajcovicova in her Introducing … Profile.
Correspondence
Biocatalysis
Correspondence on “Structural Insight into the Catalytic Mechanism of the Endoperoxide Synthase FtmOx1”
- First Published: 04 August 2023

Recently, Cen, Wang, Zhou et al. reported a crystal structure of a ternary complex of the non-heme iron endoperoxidase FtmOx1 (PDB entry 7ETK) and concluded that it provides evidence supporting the FtmOx1 catalysis CarC-like mechanistic model. However, this work did not accurately describe key mechanistic features and differences of the Carc-like and COX-like models, and their data do not support their conclusions.
Reply to Correspondence on “Structural Insight into the Catalytic Mechanism of the Endoperoxide Synthase FtmOx1′′
- First Published: 04 August 2023

The 2-oxoglutarate (2OG)-dependent non-heme enzyme FtmOx1 can catalyze the endoperoxidation of fumitremorgin B, producing verruculogen. The side product of deisoprenylation becomes the major product when the analogue 13-oxo-fumitremorgin B is used as the substrate. Fumitremorgin B and 13-oxo-fumitremorgin B show similar substrate-binding patterns with FtmOx1 but different enzymatic conversions.
Minireviews
Fluorescent Probes
Orderly Self-Assembly of Organic Fluorophores for Sensing and Imaging
- First Published: 23 May 2023

In past decades, the orderly self-assembly of functionalized fluorophores has gained much attention. Such fluorophores can form nanoaggregates by self-assembly, which prolong their residence time in vivo, achieving high signal-to-background ratios and accurate bioimaging. In this review, we summarize progress and challenges of self-assembled fluorophores, focusing on their development history, self-assembly mechanism and biomedical applications.
COF Synthesis
Beyond Solvothermal: Alternative Synthetic Methods for Covalent Organic Frameworks
- First Published: 02 June 2023

We present a comprehensive overview of the recent synthetic advancements of covalent organic frameworks (COFs), with emphasis on the energy input required. These emerging strategies encompass microwave-assisted, sonochemical, mechanochemical, photochemical, plasma-promoted, electric field-induced, and electron beam-mediated synthesis. We also delve into the merits and limitations of these methods in comparison to the solvothermal approach.
Reviews
Cage Compounds
About Perfluoropolyhedranes, Their Electron-Accepting Ability and Questionable Supramolecular Hosting Capacity
- First Published: 20 May 2023

Symmetry infers perfection and perennity, order, and harmony. Synthesizing perfluoropolyhedranes, a serious challenge, greatly enhances polyhedrane electron affinity, providing a unique opportunity for hosting an extra electron inside a molecular frame. The expectations for an easy entry to supramolecular chemistry hinted by such “cage” or “box” structures are, however, illusive.
Li Batteries
40 Years of Low-Temperature Electrolytes for Rechargeable Lithium Batteries
- First Published: 15 May 2023
Research Articles
Polymerization
Facile Synthesis of Linear and Cyclic Poly(diphenylacetylene)s by Molybdenum and Tungsten Catalysis
- First Published: 27 June 2023

Two improved methods for synthesis of poly(diphenylacetylene)s having functional groups have been developed. Molybdenum(V) catalysis with the MoCl5-PhSnnBu3 system provides linear poly(diphenylacetylene)s by migratory insertion polymerization while low-valent tungsten catalysis with the WCl4-Ph4Sn-PPh3 system provides cyclic poly(diphenylacetylene)s by ring expansion polymerization.
CO2 Reduction Reaction | Hot Paper
Molecular Engineering of Cation Solvation Structure for Highly Selective Carbon Dioxide Electroreduction
- First Published: 28 July 2023

A versatile molecular engineering strategy for regulating the solvation shell of metal cations has been reported, aiming to achieve a balanced H2O activation behavior. By enriching the interface with aprotic organic molecules, the density of H2O is decreased, and a second-sphere effect is delivered to stabilize the adsorbed H2O molecule, leading to highly selective CO2 electroreduction.
Organic Semiconductors
Extremely Electron-Withdrawing Lewis-Paired CN Groups for Organic p-Dopants
- First Published: 04 June 2023

The use of various CN-functionalized conjugated molecules and Lewis acids has led to the synthesis of unprecedentedly strong organic p-dopants (LUMO level down to −5.93 eV) exhibiting excellent doping stability (over 40 h at 120 °C). Lewis pairing leads to the electron-withdrawing properties of the CN groups increasing almost twofold and the dopant size enlarging significantly.
Hybrid Materials
Anomalous Charge Transfer from Organic Ligands to Metal Halides in Zero-Dimensional [(C6H5)4P]2SbCl5 Enabled by Pressure-Induced Lone Pair-π Interaction
- First Published: 18 July 2023

Efficient charge transfer from organic ligands to metal halides in zero-dimensional organic metal halide hybrids [(C6H5)4P]2SbCl5 is achieved through pressure modulation. It leads to high excitonic emission with near-unity photoluminescence quantum yield. In situ experimental and theoretical methods show that the pressure-induced electronic coupling between the lone-pair electrons of Sb3+ and the π electrons of benzene acts as an unexpected “bridge” for the charge transfer.
Cycloaddition Reactions | Hot Paper
Tetrazole Diversification of Amino Acids and Peptides via Silver-Catalyzed Intermolecular Cycloaddition with Aryldiazonium Salts
- First Published: 22 May 2023
NMR spectroscopy | Very Important Paper
Elongated Bacterial Pili as a Versatile Alignment Medium for NMR Spectroscopy
- First Published: 29 May 2023

A new, liquid-crystalline alignment medium for the measurement of residual dipolar couplings by NMR spectroscopy is presented. The medium is based on filamentous type 1 pili from E. coli and shown to withstand a wide range of challenging experimental conditions. Being compatible with biological macromolecules and small molecules alike, its high versatility suggests broad applicability in molecular structure determination by NMR.
Synthetic Biology
Secretion-Catalyzed Assembly of Protein Biomaterials on a Bacterial Membrane Surface
- First Published: 20 July 2023

Bacillus subtilis can be programmed to autonomously assemble recombinant silk peptides on its own membrane, and then release them as fibers into the extracellular milieu. The process, called secretion-catalyzed assembly, enables coupled synthesis, assembly, and processing of biomaterials by microbes.
Organocatalysis
Asymmetric (4+n) Cycloadditions of Indolyldimethanols for the Synthesis of Enantioenriched Indole-Fused Rings
- First Published: 22 June 2023

The first catalytic asymmetric (4+2) and (4+3) cycloadditions of 2,3-indolyldimethanols enable the construction of enantioenriched indole-fused rings in high yields with excellent enantioselectivities. This approach led to the first enantioselective construction of challenging tetrahydroindolocarbazole scaffolds, which show promising anticancer activity. Theoretical calculations offer an in-depth understanding of this class of indolylmethanols.
Reverse Water–Gas Shift
Platinum and Frustrated Lewis Pairs on Ceria as Dual-Active Sites for Efficient Reverse Water-Gas Shift Reaction at Low Temperatures
- First Published: 21 July 2023

Dual-active sites comprising Pt clusters and frustrated Lewis pairs (FLP) on porous CeO2 nanorods provide an interface-independent pathway to boost the reverse water-gas shift reaction at low temperatures. The FLP sites enable strong adsorption of CO2 for efficient activation, but weak adsorption of CO that suppresses CH4 formation.
Asymmetric Catalysis
Host-Guest Systems | Hot Paper
Mechanically Interlocked [2]Rotaxane Aerogels with Tunable Morphologies and Mechanical Properties
- First Published: 28 July 2023

The potential of mechanical bonds in modulating the intrinsic characteristics of aerogels, such as porous microstructures and mechanical performances, has been demonstrated with mechanically interlocked aerogels. Such networks facilitate the development of smart materials with complex functionalities.
Peptides
Intracellular Molecules Induced Extracellular Peptide Self-Assembly for Efficient and Effective In Situ Cell Purification
- First Published: 22 July 2023

Unavoidable leaky protein expression limits in situ cell purification of synthetic mRNA switches. Harnessing the power of controlled self-assembly, we use synthetic mRNA switch to convey intracellular biomarker information into enzyme-controlled toxic assemblies only on the surface of undesired cells, promising high purity and high retention of target cells.
Renewable Polymers | Very Important Paper
Modular Alcohol Click Chemistry Enables Facile Synthesis of Recyclable Polymers with Tunable Structure
- First Published: 25 July 2023
Fuel Cells
Migration and Precipitation of Platinum in Anion-Exchange Membrane Fuel Cells
- First Published: 18 July 2023

Using the complementary techniques of X-ray micro-computed tomography, scanning electron microscopy and energy dispersive X-ray spectroscopy, Pt ion migration was identified as an important factor to explain the decay in performance of anion-exchange membrane (AEM) fuel cells. The picture shows 3D reconstruction micro-CT images of the cross-section MEAs with Sustainion AEM and Pt/C cathode electrode after (a) 5 h and (b) 70 h of operation at 0.15 A/cm2.
Chlorine Batteries | Very Important Paper
Unlocking Reversible Silicon Redox for High-Performing Chlorine Batteries
- First Published: 16 July 2023

Reversible Si redox has been unlocked in Cl-based batteries through rational electrolyte dilution and anode passivation, which demonstrates excellent electrochemical performance and high practicability. It enables us to revisit the overlooked Cl-based batteries and to harness them for sustainable and high-performance energy storage.
Chiral Hybrid Metal Halides
Integrating Achiral and Chiral Organic Ligands in Zero-Dimensional Hybrid Metal Halides to Boost Circularly Polarized Luminescence
- First Published: 24 July 2023

We propose an efficient strategy to achieve simultaneously high photoluminescence quantum yield and large dissymmetry factor (glum) in chiral 0D hybrid metal halides by integrating achiral and chiral ligands. A pair of (R/S-MBA)2(Gua)4(In0.99Sb0.01Cl6)2 H2O (MBA=α-methylbenzylammonium, Gua=guanidine) HMHs with near-unity PLQYs and large glum values (~0.01) are constructed.
Copper Nanoclusters
Total Structure, Electronic Structure and Catalytic Hydrogenation Activity of Metal-Deficient Chiral Polyhydride Cu57 Nanoclusters
- First Published: 19 July 2023
Immunotherapy
Bioorthogonal Reaction-Mediated Tumor-Selective Delivery of CRISPR/Cas9 System for Dual-Targeted Cancer Immunotherapy
- First Published: 23 July 2023

A tumor-targeted CRISPR/Cas delivery strategy was developed to switch on antitumor immunity via bioorthogonal reaction. Selectively labeling tumor sites and the activation of the cGAS-STING pathway was achieved first, turning “cold” tumors into “hot”. The targeted accumulation of the CRISPR/Cas system within tumors via click chemistry then further enhanced cancer immunotherapy, substantially boosting antitumor effectiveness.
Carbene Chemistry
Reductive Catalytic Difluorocarbene Transfer via Palladium Catalysis
- First Published: 26 June 2023

A new mode of difluorocarbene transfer reaction that tames difluorocarbene to couple with two electrophiles via palladium catalysis has been developed. This reaction overcomes the intrinsic limitations of electrophilic difluorocarbene and allows difluoromethylation of various aryl bromides and aryl triflates. Experimental mechanistic studies revealed that a palladium(0/II) pathway is responsible for this reductive reaction.
Electrocatalytic H2O2 Production
Cyclodextrin-supported Co(OH)2 Clusters as Electrocatalysts for Efficient and Selective H2O2 Synthesis
- First Published: 05 July 2023
Lithium Batteries
Olefin-Linked Covalent Organic Frameworks with Electronegative Channels as Cationic Highways for Sustainable Lithium Metal Battery Anodes
- First Published: 24 July 2023

Olefin-linked covalent organic frameworks (COFs) with electronegative 1D channels are presented as a cationic highway membrane strategy for sustainable Li metal battery anodes. Introduction of triazine rings and fluorinated groups into the COF skeletons played a viable role in enhancing salt dissociation and guiding uniform Li+ flux within the channels. The resulting COF membrane exhibited reliable Li plating/stripping cyclability and stable capacity retention in the Li/LiFePO4 full cell.
Polymer Degradation | Very Important Paper
Regulating Degradation Pathways of Polymers by Radical-Triggered Luminescence
- First Published: 25 July 2023

We have proposed the radical-triggered luminescence to monitor the radical behaviours during polymer degradation. It was disclosed that the pure polymers showed a single sigmoidal dynamic curve from ROO⋅ emissions, leading to the exponential proliferation for the degradation evolution. Alternatively, the degradation pathways of polymers were regulated into a double sigmoidal curve by anti-degradation LDHs.
C-H Functionalization
Remote C−H Olefination of Heterocyclic Biaryls Enabled by Reversibly Bound Templates
- First Published: 20 July 2023
Synthetic Methods
A Modular Approach for the Synthesis of Natural and Artificial Terpenoids
- First Published: 13 July 2023

A robust chem-stamp approach consisting of two steps, one-carbon extension of aldehydes to alkenyl boronates and the rhodium-catalyzed reaction of these alkenyl boronates with 2,3-allenols, has been developed for the construction of key isoprene units in terpenoids. This approach enables the modular concise synthesis of terpenoids and the creation of artificial terpenoids with control over the number of isoprene units, the side chain, and two terminal groups.
Photocatalytic H2O Splitting
Bottom-up Synthesis of Single-Crystalline Poly (Triazine Imide) Nanosheets for Photocatalytic Overall Water Splitting
- First Published: 18 July 2023
Molecular Glues | Hot Paper
From Tethered to Freestanding Stabilizers of 14-3-3 Protein-Protein Interactions through Fragment Linking
- First Published: 16 July 2023

Linked fragments for molecular glue development for the 14-3-3/ERα protein-protein interactions (PPIs) are described. Two classes of fragments were co-crystallized and subsequently linked, resulting in a noncovalent hybrid molecule that was further optimized, guided by 20 crystal structures, resulting in a selective 25-fold stabilization of the 14-3-3/ERα PPIs.
PROTACs | Very Important Paper
Nano Proteolysis Targeting Chimeras (PROTACs) with Anti-Hook Effect for Tumor Therapy
- First Published: 24 July 2023
Biosensors | Very Important Paper
Main Group Chemistry | Hot Paper
Coordination and Activation of N2 at Low-Valent Magnesium using a Heterobimetallic Approach: Synthesis and Reactivity of a Masked Dimagnesium Diradical
- First Published: 20 July 2023

Reduction of a bulky magnesium(II) diamide with 5 % w/w K/KI under an N2 atmosphere has given a complex between magnesium and doubly reduced dinitrogen, N22−. The reaction has been calculated to proceed via an anionic magnesium(I) radical, and the final product shown to act as a masked dimagnesium(I) diradical in reactions with CO, H2 and C2H4.
Homogeneous Catalysis | Hot Paper
Correlating Metal Redox Potentials to Co(III)K(I) Catalyst Performances in Carbon Dioxide and Propene Oxide Ring Opening Copolymerization
- First Published: 06 July 2023

Carbon dioxide and propene oxide ring opening copolymerization is a leading carbon dioxide utilization technology. Future catalyst development needs better understanding of how to maximize both activity and selectivity. Here, a series of catalysts show a correlation between both their activity and selectivity values with the cobalt reduction potential, providing a useful ‘predictive’ tool for catalyst performances.
Polymerization | Hot Paper
A Strategy for Controlling the Polymerizations of Thiyl Radical Propagation by RAFT Agents
- First Published: 21 July 2023

A new strategy that could enable the polymerizations of thiyl radical propagation to be controlled by existing RDRP methods has been reported. The key to this strategy is the propagating thiyl radicals could undergo desulfurization with isocyanides to generate stabilized alkyl radicals, thereby allowing for controlling the polymerization via RAFT agents, leading to the formation of main-chain polymers with well-defined architectures.
Gas Separation | Very Important Paper
Pore Modulation of Hydrogen-Bonded Organic Frameworks for Efficient Separation of Propylene
- First Published: 24 July 2023

A series of HOFs with unique pore structures have been designed by precise pore modulation engineering through the introduction of structure directing agents. One example is HOF-ZSTU-2 with a one-dimensional pearl-chain channel that balances size control, adsorption capacity, and functional sites for efficient storage and separation of propylene.
Fluorine Chemistry
Nickel-Catalyzed Selective C(sp2)−F Bond Alkylation of Industrially Relevant Hydrofluoroolefin HFO-1234yf
- First Published: 20 July 2023

A nickel-catalyzed selective C(sp2)−F bond alkylation of the inexpensive industrial chemical HFO-1234yf with alkylzinc reagents has been developed. Preliminary mechanistic studies reveal that the less electron-rich pyridine-oxazoline or bipyridine-based ligands feature comparable or even higher rates of C−F bond oxidative addition than the electron-rich phosphine ligands in the presence of lithium bromide.
Thermo-Photoresponsive MOFs | Very Important Paper
Cooperative and Orthogonal Switching in the Solid State Enabled by Metal-Organic Framework Confinement Leading to a Thermo-Photochromic Platform
- First Published: 24 July 2023

Like two color-changing chameleons coming face to face, integration of two distinct stimuli-responsive moieties within the same platform results in their synergistic behavior. Perturbation of the chameleons’ environment upon a different external stimulus breaks the synergy, promoting their orthogonal behavior, a concept highlighted for a novel hierarchical photo-thermo-responsive metal–organic framework.
Li Metal Batteries | Very Important Paper
Designing F/P Hybrid Polymer as Ultrastable Cationic Shielding Interphase for High-Performance Lithium Metal Batteries
- First Published: 26 July 2023

We reported the on-demand development of phosphonium fluoropolymers as the electrostatic shielding interlayer to stabilize Li metal anodes, where the periodic arrangement of F/P units not only adaptively homogenized electric field distribution to induce dendrite-free Li deposition, but also restrained undesirable coating decomposition to provide persistent protection for long-term battery cycling.
Li–S batteries
An Endogenous Prompting Mechanism for Sulfur Conversions Via Coupling with Polysulfides in Li−S Batteries
- First Published: 19 July 2023

Traditional sulfur conversion reactions suffer from severe shuttle effects as well as sluggish redox kinetics. Here, we achieved an endogenous facilitation mechanism for sulfur conversion which constructed a fast “internal cycle” of the promotors to promote the slow “external cycle” of sulfur conversions by coupling lithium polysulfides with functional molecules. By regulating the intermediates solubility and mediating the reaction kinetics, organophosphorus polysulfides as endogenous promotors can simultaneously eliminate the shuttle effect and improve the sulfur electrode process.
Chirality
Supramolecular Block Copolymers from Tricarboxamides. Biasing Co-assembly by the Incorporation of Pyridine Rings
- First Published: 22 July 2023

The co-assembly of the pyridine-based tricarboxamides 2–4 with tricarboxamide 1 is investigated. Whilst the formation of the supramolecular co-polymer poly-1-co-2 is not possible, co-polymers poly-1-co-3 and poly-1-co-4 are formed. The latter has been investigated by mass-balance model that revealed an alternating blocky microstructure.
Supramolecular Polymers | Hot Paper
One-Step Manufacturing of Supramolecular Liquid-Crystal Elastomers by Stress-Induced Alignment and Hydrogen Bond Exchange
- First Published: 27 July 2023

Supramolecular soft actuators have been developed that are based on hydrogen-bond crosslinked liquid-crystal elastomers (LCEs). The LCEs can be manufactured in the form of fibers and 2D/3D objects that are capable of performing stable and reversible thermal actuation under mechanical stretch or melt extrusion, opening the way for the one-step and custom manufacturing of soft actuators.
Solid-State Batteries | Very Important Paper
Polymers with Intrinsic Microporosity as Solid Ion Conductors for Solid-State Lithium Batteries
- First Published: 21 July 2023

Electrolytes based on polymers with intrinsic microporosity (PIMs) are proposed as ideal solid electrolytes for lithium batteries. Benefiting from rational material selection and structure design, solid-state Li−O2 batteries deliver high discharge specific capacity (11307 mAh g−1) and prolonged cycling life (247 cycles). The solid-state Li-metal batteries can operate steadily for over 100 cycles after a series of abuse tests (bending and twisting).
Mg-Ion Batteries | Very Important Paper
Proton/Mg2+ Co-Insertion Chemistry in Aqueous Mg-Ion Batteries: From the Interface to the Inner
- First Published: 24 July 2023

Proton co-insertion into tunnel materials is determined jointly by interface derivation and inner diffusion. At the electrode-electrolyte interface, hydrated Mg2+ has poor insertion kinetics and thus accumulates on the surface of VO2(B) to hydrolyze, triggering the formation of Mg-rich SEI and production of protons. In the tunnels, co-inserted/lattice H2O molecules block the Mg2+ diffusion while facilitate proton diffusion.
Heterogeneous Catalysis | Hot Paper
Coordination Defect-Induced Frustrated Lewis Pairs in Polyoxo-metalate-Based Metal–Organic Frameworks for Efficient Catalytic Hydrogenation
- First Published: 24 July 2023

A coordination defect-induced strategy gives frustrated Lewis pair (FLP) sites in a polyoxometalate (POM) based metal–organic framework (MOF), where the Lewis acid (LA) sites are linker-defective metal nodes and the Lewis base (LB) sites are derived from surface oxygen atoms of the POM. This FLP catalyst achieved heterolytic dissociation of H2 into highly active Hδ−, thus exhibiting excellent activity in acetylene hydrogenation.
Lithium-Ion Batteries
Semi-Metallic Superionic Layers Suppressing Voltage Fading of Li-Rich Layered Oxide Towards Superior-Stable Li-Ion Batteries
- First Published: 30 July 2023

Li-rich layer oxide (LRLO) cathodes with semi-metallic superionic layers are prepared via a simple one-step modification. The inner semi-metallic LiMn2O4-like structure (LMO), has spin-polarized conducting electrons that can bond with oxygen, preventing oxygen release. The outer fast-ion conductor Li0.8Nb0.96Ni0.2O3 (LNO) acts as a fast-ion conductor facilitating Li+ migration and alleviating metal dissolution.
Host–Guest Systems | Very Important Paper
Insights into the Correlation of Cross-linking Modes with Mechanical Properties for Dynamic Polymeric Networks
- First Published: 25 July 2023

Based on comprehensive comparison on mechanical properties between dually cross-linked network and individual covalent or supramolecular cross-linked network, we reveal that the dual cross-linking mode can combine the advantages of covalent cross-links and supramolecular cross-links, exhibiting not only quick deformation recovery, outstanding breaking stress and puncture resistance, but also excellent toughness and energy dissipation ability.
Gas Separation
Balancing the Crystallinity and Film Formation of Metal–Organic Framework Membranes through In Situ Modulation for Efficient Gas Separation
- First Published: 24 July 2023

The balance between crystallinity and film-formation of metal–organic framework (MOF) membrane is demonstrated for the first time using a facile in situ modulation strategy. Through competitive complexation with a ligand, acetic acid systematically reduces the crystallinity and optimizes the film formation of the MOF membrane, influencing its gas separation properties.
Perovskite Electrocatalysts
Accelerated Surface Reconstruction through Regulating the Solid-Liquid Interface by Oxyanions in Perovskite Electrocatalysts for Enhanced Oxygen Evolution
- First Published: 20 July 2023

To promote the spontaneous chemical reaction process of LaNiO3−δ, the oxyanions were added into electrolytes to regulate the solid–liquid interface. The oxyanions adsorb onto the solid–liquid interface, disrupting the dynamic equilibrium between the adsorbed OH− ions and the OH− ions generated during surface reconstruction. It could be an effective way to accelerate surface reconstruction process.
Organic chemistry | Hot Paper
Synergistic Palladium/Lewis Acid-Catalyzed Regio- and Stereo-divergent Bissilylation of Alkynoates: Scope, Mechanism, and Origin of Selectivity
- First Published: 21 July 2023

A Pd-catalyzed divergent bissilylation of alkynoates using disilane reagent TMDQ (see TOC graphic) is presented. Reversed regio- and stereo-selectivity was obtained through addition of Lewis acids. MAD (methylaluminum bis(2,6-di-t-butyl-4-methylphenoxide) impacted electronically-favored migratory insertion through steric effect while the addition of BCF (tris(pentafluorophenyl)borane) allowed reductive elimination as the rate-determining step.
Photochemistry | Hot Paper
One/Two-Photon-Excited ESIPT-Attributed Coordination Polymers with Wide Temperature Range and Color-Tunable Long Persistent Luminescence
- First Published: 24 July 2023

One/two-photon-excited long persistent luminescence (LPL) was obtained in an ESIPT-attributed CdII coordination polymer (LIFM-106) with wide temperature range (100–380 K) and color tunability. Comparative study manifests the rational ligand modification and J-aggregation in LIFM-106 enhances the competitiveness of monomer LPL to counter-balance the excimer emission.
Tandem Catalysis | Hot Paper
Xylene Synthesis Through Tandem CO2 Hydrogenation and Toluene Methylation Over a Composite ZnZrO Zeolite Catalyst
- First Published: 28 July 2023

Selective xylene synthesis from CO2 hydrogenation was achieved by regulating the interaction between two active components of a composite catalyst through a toluene-containing coupling reaction. The relationship between ZnZrO and the zeolite involved in the promotion effect was explored with detailed characterization.
Electrochemistry | Hot Paper
Highly Efficient Biomass Upgrading by a Ni−Cu Electrocatalyst Featuring Passivation of Water Oxidation Activity
- First Published: 24 July 2023

A novel bimetallic Ni−Cu electrode for the oxidation of 5-hydroxymethyl furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) with an industrial-scale current density of up to 1000 mA cm−2 has been successfully developed. Superior stability and activity of the prepared electrode enable the gram-scale production of FDCA with a very high overall yield, purity, and Faradaic efficiency.
Asymmetric Catalysis
A Nuclearity-Dependent Enantiodivergent Epoxide Opening via Enthalpy-Controlled Mononuclear and Entropy-Controlled Dinuclear (Salen)Titanium Catalysis
- First Published: 25 July 2023

A nuclearity-dependent enantiodivergent epoxide opening reaction has been developed based on a mononuclear (salen)TiIII complex and its self-assembled oxygen-bridged dinuclear counterparts within the same stereogenic ligand scaffold. Mechanistic studies reveal that the nuclearity-distinct catalysts regulate the enthalpy and entropy controlling modes in the enantiodifferentiation process to achieve profound chirality inversion.
Gas Separation
Polymer Folding | Hot Paper
Visible-Light-Induced Control over Reversible Single-Chain Nanoparticle Folding
- First Published: 23 July 2023

Bimanes allow the synthesis of water-soluble single-chain nanoparticles (SCNPs) and enable the effective unfolding with mild visible light from a compact structure into a linear chain. The unfolding of the fluorescent nanoparticles is reversible and occurs in aqueous systems, making it promising for controlling and tracing the SCNPs in biological environments.
EPR Spectroscopy
Time-Resolved Mn2+−NO and NO−NO Distance Measurements Reveal That Catalytic Asymmetry Regulates Alternating Access in an ABC Transporter
- First Published: 17 July 2023

Several ATP-binding cassette (ABC) transporters possess asymmetric nucleotide-binding sites (NBSs). Here, we elucidated its functional relevance using concomitant NO−NO, Mn2+−NO, and Mn2+−Mn2+ distance measurements for the ABC exporter TmrAB in a time-resolved manner. Our results shows that ATP hydrolysis at the active consensus NBS accelerates the reverse transition, and the impaired degenerate NBS might regulate the overall kinetics of this process.
Communications
Light-to-Chemical Conversion | Hot Paper
A Broad Light-Harvesting Conjugated Oligoelectrolyte Enables Photocatalytic Nitrogen Fixation in a Bacterial Biohybrid
- First Published: 12 July 2023

We developed a new strategy to enable light-driven nitrogen fixation in non-photosynthetic bacteria by integrating the novel conjugated oligoelectrolyte COE-IC into A. vinelandii. Upon excitation of light, COE-IC generates electron equivalents at the abiotic-biotic interface. These photoelectrons are then transferred to nitrogenase, which drives the reduction of dinitrogen to ammonia.
Allylic Compounds
Regioselective Formal β-Allylation of Carbonyl Compounds Enabled by Cooperative Nickel and Photoredox Catalysis
- First Published: 04 May 2023
Organic Electronics | Hot Paper
Organic Electrochemical Transistor Based on Hydrophobic Polymer Tuned by Ionic Gels
- First Published: 13 July 2023

An ionic gel interfacial layer is applied to improve the ionic transport of the hydrophobic conjugated polymers in organic electrochemical transistors (OECTs). With this approach, hydrophobic conjugated polymers could be used directly, while the types and ratios of gel matrix and ionic liquids in the ionic gels could be tuned to achieve optimal OECT properties for improved performance.
Water Splitting | Very Important Paper
Rh/Cr2O3 and CoOx Cocatalysts for Efficient Photocatalytic Water Splitting by Poly (Triazine Imide) Crystals
- First Published: 10 May 2023
Atropisomers
Enantioselective Synthesis of N−N Biaryl Atropisomers through Iridium(I)-Catalyzed C−H Alkylation with Acrylates
- First Published: 04 May 2023

A highly efficient iridium-catalyzed asymmetric C−H alkylation reaction is described. A series of structurally diverse indole-pyrrole and pyrrole-pyrrole N−N atropisomers were obtained in good yields (up to 98 %) with excellent enantioselectivity (up to 99 % ee). This reaction features perfect atom economy, wide substrate scope, and multifunctionalized products allowing diverse transformations.
Polymerization
Topochemical Syntheses of Polyarylopeptides Involving Large Molecular Motions: Frustrated Monomer Packing Leads to the Formation of Polymer Blends
- First Published: 24 July 2023

Introduction of aryl rings in the backbone of polymer chains is one of the key strategies to improve the chain rigidity and hence the properties. In peptide chemistry the technique gave birth to a new class of molecular systems called arylopeptides. Here we discuss the synthesis of polyarylopeptides, peptide polymers with periodic aryl units, from amino acid-based monomers via topochemical azide-alkyne cycloaddition polymerization.
Chiral Amplification
Stereoselective Plasmonic Interaction in Peptide-tethered Photopolymerizable Diacetylenes Doped with Chiral Gold Nanoparticles
- First Published: 22 July 2023

Peptide-tethered diacetylene monomers exhibit efficient topochemical photopolymerization and allow control over the chiroptical properties of the resulting chiral polydiacetylenes. Achiral and chiral gold nanoparticles were incorporated in the chiral polymers and the stereoselective plasmonic interactions investigated, with the ultimate goal of designing next-generation organic–inorganic hybrid materials with large chiroptic effects.
Syngas Conversion
Insights into the Diffusion Behaviors of Water over Hydrophilic/Hydrophobic Catalysts During the Conversion of Syngas to High-Quality Gasoline
- First Published: 20 July 2023

A bifunctional catalyst composed of hydrophobic FeNa@Si-c and HZSM-5 zeolite converts syngas to gasoline with high selectivity. The diffusion of water molecules through a hydrophilic catalyst is bidirectional, while the diffusion through a hydrophobic catalyst is unidirectional, thereby allowing control of syngas-to-gasoline side reactions related to water.
Nanoparticles
Isostructural Nanocluster Manipulation Reveals Pivotal Role of One Surface Atom in Click Chemistry
- First Published: 20 July 2023

Single-atom modifications are typically accompanied by appreciable changes to the overall particle's structure. Herein, we demonstrate surface single-atom manipulation based on [Cu58H20PET36(PPh3)4]2+ (Cu58; PET: phenylethanethiolate; PPh3: triphenylphosphine), leading to the isostructural analogue [Cu57H20PET36(PPh3)4]+ (Cu57). Remarkably, this single surface atom drastically alters the catalytic reactivity of the nanoclusters.
Total Synthesis | Hot Paper
A Homo-Mannich Reaction Strategy Enables Collective Access to Ibophyllidine, Aspidosperma, Kopsia, and Melodinus Alkaloids
- First Published: 25 July 2023

A homo-Mannich reaction of cyclopropanol with an iminium ion, generated by an asymmetric allylic dearomatization of indole, has been developed to construct a tricyclic hydrocarbazole core. This approach enables a collective asymmetric synthesis of ibophyllidine, Aspidosperma, Kopsia, and Melodinus alkaloids having either a five-, six-, or seven-membered E ring.
Supramolecular Chemistry | Hot Paper
Chiral Adaptive Induction of an Achiral Cucurbit[8]uril-Based Supramolecular Organic Framework by Dipeptides in Water
- First Published: 19 July 2023

An unexpected chiral adaptive induction of an achiral CB[8]-based supramolecular organic framework (SOF) was explored, exhibiting the opposite CD and CPL spectra in the presence of L-TrpTrp and L-PhePhe, respectively. Furthermore, this SOF demonstrates the sequence-selective chiral induction for sequences-opposite Trp-/Phe-containing dipeptides, allowing for the discrimination and differentiation of these dipeptide sequences.
Gas-Phase Chemistry
Hydrogen-Atom Tunneling in a Homochiral Environment
- First Published: 19 July 2023

How would a chiral environment impact the dynamics of hydrogen atoms? Using rotational spectroscopy in combination with the solutions of a simple one-dimensional Schrödinger equation approach, we revealed the intriguing distinctions of hydrogen atom dynamics between homochiral and heterochiral dimers of trans-1,2-cyclohexanediol.
Host-Guest Systems
A Redox-Responsive Ferrocene-Based Capsule Displaying Unusual Encapsulation-Induced Charge-Transfer Interactions
- First Published: 05 July 2023

Quantitative assembly of bent amphiphiles with two ferrocene units leads to a ferrocene-based capsule in water. Besides redox-responsive disassembly/assembly properties, the new capsule displays unusual host-guest charge-transfer (CT) interactions upon encapsulation of electron-accepting molecules in the multi-ferrocene cavity. The CT interactions are facilely dissociated by a redox-triggered stimulus.
Luminescence
Achieving Color-Tunable Long Persistent Luminescence in Cs2CdCl4 Ruddlesden-Popper Phase Perovskites
- First Published: 20 July 2023

The long persistent luminescence (LPL) of 2D Cs2CdCl4 Ruddlesden-Popper phase perovskites based on the self-assembled 2D interlayer galleries structure is investigated. Through doping engineering, the LPL decay time is increased, the emission color is adjustable, and the thermal stability of PL is enhanced dramatically. Furthermore, we highlight the promising applications of Cs2CdCl4 perovskite systems in advanced anti-counterfeiting.
Organic Electrode Materials | Hot Paper
Long-Life, High-Rate Rechargeable Lithium Batteries Based on Soluble Bis(2-pyrimidyl) Disulfide Cathode
- First Published: 23 July 2023

Bis(2-pyrimidyl) disulfide (Pym2S2) has proven to be a high rate cathode material for rechargeable lithium batteries. The superdelocalization of pyrimidyl groups is reducing the S−S bond dissociation energy, which depletes the intrinsic energy barrier of dissociated electron transfer. The lithium half cell achieves 2000 cycles at 5 C. In addition, the cell shows a capacity retention of 78.0 % after 500 cycles at 30 C.
Electrosynthesis | Hot Paper
Electrochemical Gold-Catalyzed 1,2-Difunctionalization of C−C Multiple Bonds
- First Published: 25 July 2023

The first report on electrochemical AuI/AuIII catalysis for 1,2-difunctionalization of C−C multiple bonds has been presented. This external-oxidant-free approach utilizes the anodic oxidation of vinyl-AuI to vinyl-AuIII complexes to achieve oxy-alkynylation of allenoates to access alkyne-substituted butenolides in an undivided cell.
Fluorine Chemistry | Hot Paper
Copper-Catalyzed Enantioselective Difluoromethylation-Alkynylation of Olefins by Solving the Dilemma between Acidities and Reduction Potentials of Difluoromethylating Agents
- First Published: 19 July 2023

The linear relationship between reduction potential differences (ΔE) and substituent constants (σ) of aryl difluoromethyl sulfones provides a powerful strategy to solve the dilemma of acidities and reduction potentials of difluoromethylating agents. The strategy enabled achieving enantioselective difluoromethylation-alkynylation reactions of olefins with difluoromethyl 4-chlorophenyl sulfone.
Phosphorescent Probes
Dual-emissive Iridium(III) Complexes as Phosphorescent Probes with Orthogonal Responses to Analyte Binding and Oxygen Quenching
- First Published: 28 July 2023

We reported dual-emissive iridium(III) complexes bearing a di(2-picolyl)-amine (DPA) unit, which exhibited green and red dual phosphorescence in aqueous solutions. The complexes exhibited static and dynamic phosphorescence quenching in response to copper(II) ions and oxygen, respectively, at different wavelengths, achieving colorimetric emission response in solutions and multichannel response in live cell imaging.
Polymerization | Hot Paper
Tribochemically Controlled Atom Transfer Radical Polymerization Enabled by Contact Electrification
- First Published: 28 July 2023

Ultrasound or ball milling of piezoelectric particles to control atom transfer radical polymerization (ATRP) requires high-energy and high-frequency mechanical stimuli. Tribochemically controlled ATRP (tribo-ATRP) using titanium oxide particles and CuBr2/tris(2-pyridylmethyl)amine enables a contact-electrification catalysis (ca. 10 Hz) and gives access to a variety of polymers with predetermined molecular weights, low dispersity, and high chain-end fidelity.
Synthetic Methods
Reactivity Umpolung of Tertiary Amide Enabled by Catalytic Reductive Stannylation
- First Published: 21 July 2023

Amide carbonyl group usually serves as the electrophile, which can react with various nucleophiles. The current work shows a process to achieve the umpolung reactivity of tertiary amide carbonyl group. By leveraging this strategy, tertiary amide can react with a wide range of electrophiles to produce complex amines.