• Issue
    Volume 61, Issue 27
    July 4, 2022

Cover Pictures

Free Access

Cover Picture: Highly Fluorescent Bipyrrole-Based Tetra-BF2 Flag-Hinge Chromophores: Achieving Multicolor and Circularly Polarized Luminescence (Angew. Chem. Int. Ed. 27/2022)

  • First Published: 21 June 2022
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Advancing the construction of circularly polarized luminescence (CPL) materials by molecular design has become an important target in this research area. In their Research Article (e202204358), Yoshio Hisaeda, Toshikazu Ono, and co-workers demonstrate a new bipyrrole-based boron difluoride family exhibiting intense multicolor luminescence with easy synthetic access. Tuning the rotational barrier around the 2,2′-bipyrrole affords CPL, and multicolor CPL can be achieved by controlling the aggregation state.

Free Access

Inside Cover: Electronic Structure Changes of an Aromatic Amine Photoacid along the Förster Cycle (Angew. Chem. Int. Ed. 27/2022)

  • First Published: 13 May 2022
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Photoacids have been understood, since the pioneering work of Theodor Förster more than seven decades ago, to show a pronounced increase in acidity when electronically excited, but the underlying microscopic mechanisms have remained elusive. Sebastian Eckert et al. show in their Research Article (e202200709) how time-resolved nitrogen K-edge spectroscopy along the Förster cycle of a photoacid provides key insight into the electronic structural factors responsible for the photoacidity phenomenon.

Free Access

Inside Back Cover: Expeditious Access to Morphinans by Chemical Synthesis (Angew. Chem. Int. Ed. 27/2022)

  • First Published: 21 June 2022
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The morphinan alkaloids , especially codeine and morphine, are derived from the opium poppy and have been used for millennia for pain management. They remain vital medicines today, but climate change and geopolitical uncertainties threaten existing supply chains. In their Communication (e202203186), Martin G. Banwell, Ping Lan, and co-workers detail by far the shortest synthesis of (−)-codeine reported to date, which involves a total “in-flask” time of less than 24 hours.

Free Access

Back Cover: Catalytic Regio- and Enantioselective Protonation for the Synthesis of Chiral Allenes: Synergistic Effect of the Counterion and Water (Angew. Chem. Int. Ed. 27/2022)

  • First Published: 24 May 2022
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A chiral Lewis acid accelerated asymmetric Pudovik addition/[1,2]-phospha-Brook rearrangement is described by Shunxi Dong, Qian Peng, Xiaoming Feng, and co-workers in their Research Article (e202203650). Control experiments and theoretical calculations revealed that a synergistic effect of the counterion and water was critical for the regio- and enantioselective protonation after the [1,2]-phospha-Brook rearrangement.

Frontispiece

Free Access

Frontispiece: A Selenide Catalyst for the Activation of Alkenes through Se⋅⋅⋅π Bonding

  • First Published: 27 June 2022
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Supramolecular Catalysis In their Communication (e202203671), Yao Wang and Xinglong Yuan report the synthesis and characterization of a selenide catalyst for the activation of alkenes through Se–π bonding.

Free Access

Frontispiece: Decorating Bacteria with Triple Immune Nanoactivators Generates Tumor-Resident Living Immunotherapeutics

  • First Published: 27 June 2022
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Immunotherapeutics The development of tumor-resident living immunotherapeutics is reported by Jinyao Liu et al. in their Research Article (e202202409). The strategy is based on decorating bacteria with triple immune nanoactivators via in situ dopamine polymerization.

Graphical Abstract

Free Access

Graphical Abstract: Angew. Chem. Int. Ed. 27/2022

  • First Published: 27 June 2022

Introducing …

Free Access

Kanokwan Kongpatpanich

  • First Published: 16 May 2022
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My favorite molecule is the benzene ring because its structures and orbitals are amazing … I chose my current career path because I want to contribute to the development of my country and the scientific community … ” Find out more about Kanokwan Kongpatpanich in her Introducing … Profile.

Free Access

Dariusz W. Szczepanik

  • First Published: 19 May 2022
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I chose chemistry as a career because it explains why pencil lead and diamond are so different, but at the same time, so similar … My favorite book is “Brief Answers to the Big Questions” by Stephen Hawking …” Find out more about Dariusz W. Szczepanik in his Introducing … Profile.

Minireviews

2D Materials

Layered Organic Metal Chalcogenides (OMCs): From Bulk to Two-Dimensional Materials

  • First Published: 20 April 2022
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With metal chalcogenide layers covalently anchored by long-range ordered organic functional motifs, organic metal chalcogenides are a type of newly emerging 2D materials, which are exquisitely desired but impossible to realize by traditional methods for the synthesis of 2D materials. This Minireview gives a perspective on the structural design of bulk precursors, exfoliation methods, applications, and discusses research directions based on recently published work.

Supramolecular Chemistry

Chirality of Perylene Diimides: Design Strategies and Applications

  • First Published: 31 March 2022
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Perylene diimide has been extensively studied as a π-conjugated molecule for the construction of chiral small molecules and helical supramolecular aggregates, such as twisted ribbons and helical fibers. This Minireview discusses the strategies for designing chiral perylene diimides through chemical modifications and assembly, as well as the chiroptical and biological applications of chiral perylene diimides.

Reviews

Electrochemistry

Open Access

Electrochemistry in Magnetic Fields

  • First Published: 24 April 2022
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Conducting electrochemistry in an applied magnetic field generates forces that affect the electrochemical system due to a change in fundamental electrochemical principles. The fundamental mechanisms behind the observed changes in different applications are discussed in this Review. Suggestions on interference exclusion and possible future perspectives of magnetoelectrochemistry are also proposed.

Communications

Chalcogen Chemistry | Hot Paper

A Selenide Catalyst for the Activation of Alkenes through Se⋅⋅⋅π Bonding

  • First Published: 19 April 2022
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A new selenide catalyst was discovered and fully characterized. It was shown to be highly efficient when applied to the catalysis of alkene transformations. Several examples using this weak interaction (Se⋅⋅⋅π) catalysis were demonstrated with, in particular, the possibility of intermolecular enyne cyclizations as well as cross-coupling of triple alkenes taking place.

Solid-State Chemistry | Hot Paper

Open Access

A New Cation-Ordered Structure Type with Multiple Thermal Redistributions in Co2InSbO6

  • First Published: 31 March 2022
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Corundum-derived Co2InSbO6 undergoes an unprecedented sequence of cation rearrangements on heating, from a previously unreported ordered-R32 type distribution to two successive ordered-LiNbO3 type arrangements.

Total Synthesis

Expeditious Access to Morphinans by Chemical Synthesis

  • First Published: 07 April 2022
Description unavailable

A benchmark chemical synthesis of codeine creates an opportunity to diversify essential opiate-medicine supply chains. The brevity of this approach derives from a double-Heck cyclization reaction that generates two rings and two contiguous stereogenic carbon centres in the one pot, while a subsequent photo-redox hydroamination protocol is deployed to provide a novel, atom-economical means for assembling the morphinan piperidine D-ring.

Bioinorganic Chemistry | Very Important Paper

Open Access

A Ruthenium(II) Polypyridyl Complex Disrupts Actin Cytoskeleton Assembly and Blocks Cytokinesis

  • First Published: 13 April 2022
Description unavailable

The dinuclear RuII complex [(Ru(phen)2)2(tpphz)]4+ binds to G-actin monomers, preventing assembly into F-actin. This inhibits actin fibre assemblies within live cells and causes disruption to late cytokinesis by interfering with the function of endosomal sorting complexes required for transport (ESCRT) during abscission. These results reveal new possibilities for metal complexes as biomedical tools and novel therapeutic leads.

CO2 Reduction Reaction

Amphiphilic Polycarbonate Micellar Rhenium Catalysts for Efficient Photocatalytic CO2 Reduction in Aqueous Media

  • First Published: 20 April 2022
Description unavailable

Visible-light-induced photocatalytic CO2 reduction in aqueous media was achieved with amphiphilic polycarbonate micellar rhenium catalysts. Coordination polymers were prepared comprising amphiphilic micelles with tunable solubility in water. By adjusting the proportion of hydrophilic and hydrophobic segments, the photocatalytic system was tailored to select for CO evolution.

Synthetic Methods

anti-Selective Borylstannylation of Alkynes with (o-Phenylenediaminato)borylstannanes by a Radical Mechanism

  • First Published: 29 April 2022
Description unavailable

The first anti-borylstannylation of alkynes has been achieved by a radical mechanism with (o-phenylenediaminato)borylstannanes. This anti-addition manner is in contrast to the syn-selectivity in transition metal-catalyzed borylstannylation. 1-Boryl-2-stannylalkenes, which were applicable to sequential cross-coupling, were obtained with excellent regio- and stereoselectivity. The mechanism was revealed by DFT studies.

Polyoxometalates

Silver-Templated γ-Keggin Alkyltin-Oxo Cluster: Electronic Structure and Optical Limiting Effect

  • First Published: 27 April 2022
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The first noble-metal-templated Keggin structure, AgSn12, is prepared. The central Ag atom significantly influences the electronic structure and optical properties of the whole cluster, which have been investigated by theoretical calculations and Z-scan measurements.

Metallabenzenes | Hot Paper

Dewar Metallabenzenes from Reactions of Metallacyclobutadienes with Alkynes

  • First Published: 20 April 2022
Description unavailable

The first Dewar benzene derivative was obtained over 60 years ago. The first hetero Dewar benzene with a p-block element (a 2-Dewar pyridine) was reported 45 years ago. The first examples of structurally characterized Dewar metallabenzenes via unprecedented reactions of metallacyclobutadienes with aminoalkynes have now been successfully prepared.

Nitrogen Fixation

Open Access

Saving the Energy Loss in Lithium-Mediated Nitrogen Fixation by Using a Highly Reactive Li3N Intermediate for C−N Coupling Reactions

  • First Published: 27 April 2022
Description unavailable

A successive reaction that yields aryl imides through combining lithium-mediated N2 fixation and C−N coupling is reported. Instead of simply being hydrolyzed to NH3 with energy wasted, this work first focuses on electro-synthetic Li3N from N2-fixation for the direct synthesis of nitrogen-containing chemicals, which will compensate for the energy consumption of Li plating and make the electrochemical N2 fixation more economical.

Liquid Crystals | Hot Paper

Open Access

Tetrahedral Liquid-Crystalline Networks: An A15-Like Frank–Kasper Phase Based on Rod-Packing

  • First Published: 25 April 2022
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The first Frank–Kasper phase representing a tetrahedral network of molecular rods is reported. It is the topological dual to the Weaire–Phelan foam, being the Voronoi tessellation of the A15 sphere packing, from which this network is obtained by Delaunay triangulation.

Li-Ion Batteries

Scalable Nitrate Treatment for Constructing Integrated Surface Structures to Mitigate Capacity Fading and Voltage Decay of Li-Rich Layered Oxides

  • First Published: 20 April 2022
Description unavailable

Scalable nitrate treatment for constructing surface-integrated structure was developed to mitigate capacity fading and voltage decay. A rule for building robust surface-integrated structure is also proposed. When the binding energy of the structure locates at a low level and the Bader charge of the O atoms nearest to the cationic atoms is as small as possible, an advanced Li-rich layered oxide cathode can be obtained.

Solar Cells | Hot Paper

Vacuum-Assisted Thermal Annealing of CsPbI3 for Highly Stable and Efficient Inorganic Perovskite Solar Cells

  • First Published: 29 April 2022
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A vacuum-assisted thermal annealing approach is employed for the fabrication of CsPbI3 perovskite films with full surface coverage and enhanced crystallization. The resultant CsPbI3 perovskite solar cells exhibit a power conversion efficiency (PCE) as high as 20.06 %, along with enhanced long-term stability.

Polymerization Catalysis | Hot Paper

Open Access

Hydrophilic Catalysts with High Activity and Stability in the Aqueous Polymerization of Ethylene to High-Molecular-Weight-Polyethylene

  • First Published: 06 April 2022
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Hydrophilic sulfonated phosphinephenolato NiII catalysts are highly active and stable in aqueous ethylene polymerization, forming high molecular weight polyethylene (HDPE) dispersions with narrow particle size distributions.

Enantioseparation with COFs | Hot Paper

Chiral Covalent Organic Framework Packed Nanochannel Membrane for Enantioseparation

  • First Published: 27 April 2022
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To provide enantioselectivity in separation using nanochannel membranes, a nanochannel membrane was in situ packed with a chiral covalent organic framework (COF). The pore size of the COF matched the size of drug enantiomers. Compared with surface-modified nanochannels, the L-Tyr-COF packed nanochannels gave high enantioselectivity (94.2 %) and flux (1.33 mmol m−2 h−1), achieving an efficient enantioseparation for chiral drugs.

Nonmetallic Batteries | Hot Paper

Organic Ammonium Ion Battery: A New Strategy for a Nonmetallic Ion Energy Storage System

  • First Published: 26 April 2022
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The organic NH4+ ion batteries (OAIBs) with Prussian white (PW) as cathode and 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) as anode in a non-aqueous electrolyte were successfully designed. The batteries deliver promising electrochemical performance, which opens a new field for organic nonmetallic ion batteries.

Chemical Bonding | Hot Paper

Open Access

Bonding in a Crystalline Tri-Thorium Cluster: Not σ-Aromatic But Still Unique

  • First Published: 14 April 2022
Description unavailable

High symmetry and unusual thermodynamic stability of the recently prepared and isolated crystalline tri-thorium cluster is determined by the unique multicenter charge-shift bonding pattern (ThCl2)3 rather than the σ-aromatic Th3 bonding. The delocalized (ThCl2)3 bond extends the range of the charge-shift bonding beyond transition metals to a record seventh row of the periodic table.

Metal–Organic Frameworks | Hot Paper

Synthesis of Single-Layer Two-Dimensional Metal–Organic Frameworks M3(HAT)2 (M=Ni, Fe, Co, HAT=1,4,5,8,9,12-hexaazatriphenylene) Using an On-Surface Reaction

  • First Published: 24 April 2022
Description unavailable

1,4,5,8,9,12-Hexaazatriphenylene (HAT)-based two-dimensional conjugated metal–organic frameworks of M3(HAT)2 (M=Fe, Ni, Co) were synthesized by means of an on-surface self-assembly protocol which effectively overcomes the strong inter-molecular steric hindrance.

Circularly Polarized Luminescence | Hot Paper

Binaphthyl-Bridged Pyrenophanes: Intense Circularly Polarized Luminescence Based on a D2 Symmetry Strategy

  • First Published: 27 April 2022
Description unavailable

D2-symmetric binaphthyl-bridged pyrenophanes have been synthesized with face-to-face pyrene rings. Matching the type and position of the linkers led to the pyrenophane exhibiting intense circularly polarized luminescence with a |glum| value reaching 0.053. This effect arose because of the D2 symmetry of the dye, which resulted in the binaphthyl moieties producing a unidirectionally twisting pyrene excimer with completely parallel electric and magnetic transition dipole moments.

Fused-Ring Systems

Open Access

Doubling the Length of the Longest Pyrene-Pyrazinoquinoxaline Molecular Nanoribbons

  • First Published: 25 April 2022
Description unavailable

An iterative approach that allows doubling the length of the longest pyrene-pyrazinoquinoxaline molecular nanoribbons is reported. The largest nanoribbon obtained through this approach shows a 60 linearly-fused ring backbone (14.9 nm) and a 324-atoms core (C276N48).

Homogeneous Catalysis

Open Access

A Novel Catalytic Route to Polymerizable Bicyclic Cyclic Carbonate Monomers from Carbon Dioxide

  • First Published: 20 April 2022
Description unavailable

A novel catalytic approach for the preparation of polymerizable bicyclic carbonates allows the synthesis of a wide range of unique heterocycles. The stereochemical configuration of the epoxy alcohol substrate plays a crucial role, determining the chemoselectivity profile of this coupling manifold. The synthetic potential of these bicyclic six-membered carbonates was examined, and their successful ring-opening polymerization under mild conditions gives new incentives for relatively rigid polycarbonate architectures.

Birefringent Materials | Very Important Paper

Promising Deep-Ultraviolet Birefringent Materials via Rational Design and Assembly of Planar π-Conjugated [B(OH)3] and [B3O3(OH)3] Functional Species

  • First Published: 29 April 2022
Description unavailable

Hydroxylated π-conjugated [B(OH)3] and [B3O3(OH)3] species were proposed for designing deep-ultraviolet (DUV) birefringent materials. They show an enhanced polarizability anisotropy and HOMO–LUMO gap compared to the [BO3]3− and [B3O6]3− groups. Four DUV birefringent materials were successfully designed and synthesized under mild synthesis conditions by the assembly of planar π-conjugated [B(OH)3] and [B3O3(OH)3] functional species.

Li-Metal Batteries | Hot Paper

Additive-Assisted Hydrophobic Li+-Solvated Structure for Stabilizing Dual Electrode Electrolyte Interphases through Suppressing LiPF6 Hydrolysis

  • First Published: 25 April 2022
Description unavailable

A hydrophobic Li+-solvated structure is developed by inducing hexafluoroisopropyl acrylate (HFAC) into electrolytes, which can not only physically block the contact between PF6 and trace H2O, but also help to form an organic-rich electrode electrolyte interphase to alleviate the growth of Li dendrites and improve the structural stability of the Ni-rich cathode, resulting in improved cycling stability of Li-metal batteries.

Polymer Nanoparticle Synthesis

Scalable Synthesis of Photoluminescent Single-Chain Nanoparticles by Electrostatic-Mediated Intramolecular Crosslinking

  • First Published: 26 April 2022
Description unavailable

Fluorophore-free single-chain nanoparticles (SCNPs) and Janus derivatives were synthesized on large scale by electrostatic-mediated intramolecular crosslinking, providing a powerful tool to selectively illuminate interfaces.

Na-Ion Batteries | Hot Paper

Anomalous Redox Features Induced by Strong Covalency in Layered NaTi1−yVyS2 Cathodes for Na-Ion Batteries

  • First Published: 25 April 2022
Description unavailable

The redox voltage of doped cathodes usually falls in between the voltage of undoped layered cathodes. However, anomalous redox features were found in NaTi1−yVyS2. The discharge potential is 0.2 V higher than that of undoped cathodes. It is speculated that the anomalous voltage is mainly attributed to the strong covalency in the Ti−V−S system. Ti3+ and V3+ undergo charge transfer and form a more stable Ti (t2g0eg0) and V (t2g3eg0) electronic configuration.

Research Articles

Immunotherapy | Hot Paper

Decorating Bacteria with Triple Immune Nanoactivators Generates Tumor-Resident Living Immunotherapeutics

  • First Published: 11 April 2022
Description unavailable

Decorating bacteria with triple immune nanoactivators via in situ dopamine polymerization is reported to develop tumor-resident living immunotherapeutics. Decorated bacteria show a spatiotemporal tumor retention and a proliferation-dependent drug release, achieving potent antitumor effects in two antigen-overexpressing tumor models. This work provides a versatile platform to prepare multimodal long-acting therapeutics for tumor immunotherapy.

Single-Molecule Electronics

Strain of Supramolecular Interactions in Single-Stacking Junctions

  • First Published: 13 April 2022
Description unavailable

The strains of supramolecular interaction were explored, and revealed an odd–even effect in a series of single-stacking junctions, offering new insights into the supramolecular interaction from the molecular level.

Intermetallics

Nickel-Based High-Entropy Intermetallic as a Highly Active and Selective Catalyst for Acetylene Semihydrogenation

  • First Published: 26 April 2022
Description unavailable

Multi-metallization of intermetallic NiGa formed high-entropy intermetallics represented as (NiFeCu)(GaGe), which worked as a highly active and selective catalyst for acetylene semihydrogenation. Overhydrogenation of ethylene was completely inhibited even at complete conversion of acetylene. Moreover, the specific activity was at least five times higher than those in reported systems using selective Ni- and Cu-based catalysts.

Metal–Air Batteries

Theory-Guided Regulation of FeN4 Spin State by Neighboring Cu Atoms for Enhanced Oxygen Reduction Electrocatalysis in Flexible Metal–Air Batteries

  • First Published: 25 April 2022
Description unavailable

First-principles calculations show a nearly linear correlation of the energy barriers of critical oxygen reduction reaction (ORR) steps with the Fe magnetic moment of Fe-N-C composites. This is indeed observed when single Cu sites are incorporated into Fe−N−C aerogels, where the interactions between adjacent Fe−Cu 3d electrons result in a reduced magnetic moment of the Fe center and hence enhanced ORR activity.

Nanozymes

A Valence-Engineered Self-Cascading Antioxidant Nanozyme for the Therapy of Inflammatory Bowel Disease

  • First Published: 22 April 2022
Description unavailable

A valence-engineered strategy to develop self-cascading nanozymes with simultaneous multiple antioxidant activities has been proposed. Nanozyme LiMn2O4 (LM), as the final optimized material, exhibits the best SOD-like, CAT-like, GPx-like, and hydroxyl radical scavenging activities. The outstanding antioxidant capacity of LM was demonstrated at the cellular level and in the treatment of inflammatory bowel disease in mice.

Photopharmacology | Very Important Paper

Open Access

Computational Design, Synthesis, and Photochemistry of Cy7-PPG, an Efficient NIR-Activated Photolabile Protecting Group for Therapeutic Applications

  • First Published: 19 February 2022
Description unavailable

The computational design and synthesis of Cy7-PPG, a new oxygen-independent novel near-infrared photolabile protecting group (PPG) is reported. Cy7-PPG is the most redshifted PPG to date (λmax=746 nm), with unmatched near-infrared molecular absorptivity and aqueous solubility, and excellent uncaging efficiency, paving the way for the use of PPGs in the clinic.

Analytical Methods | Very Important Paper

Enhanced Blue Afterglow through Molecular Fusion for Bio-applications

  • First Published: 30 March 2022
Description unavailable

We developed a molecular fusion strategy to achieve a high-efficiency photochemical afterglow system. The afterglow quantum yield was up to 2.59 %, which was significantly higher than that achieved with the physical mixing strategy and the covalent coupling strategy. This afterglow system was further used for high SNR bio-imaging and for the background-free high-sensitivity lateral flow immunoassay detection of β-hCG.

Single-Atom Catalysis | Hot Paper

Electronically Engineering Water Resistance in Methane Combustion with an Atomically Dispersed Tungsten on PdO Catalyst

  • First Published: 16 April 2022
Description unavailable

Methane combustion generates less CO2 emissions than coal and oil, making it a cleaner alternative to other fossil fuels. A PdW1/Al2O3 single-atom catalyst shows enhanced H2O-resistance during CH4 combustion. The results show that catalytic CH4 combustion involves water and proceeds via a hydroperoxyl-promoted reaction on the catalyst surface. An upshift of the d-band center of Pd aids the adsorption and activation of oxygen on the catalyst.

Peptide Assemblies | Hot Paper

Programmed Supramolecular Assemblies Using Orthogonal Pairs of Heterodimeric Coiled Coil Peptides

  • First Published: 12 April 2022
Description unavailable

A novel strategy for constructing peptide-based supramolecular assemblies with pre-determined oligomeric states and topologies is reported. By using four polypeptide chains that form two orthogonal heterodimeric coiled coils and pre-installing covalent linkages between the non-complementary pairs in strategic arrangements, several discrete supramolecular assemblies with pre-determined molar masses and topologies were constructed.

Li-Ion Batteries

Open Access

Introducing 4s–2p Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium-Ion Batteries

  • First Published: 25 April 2022
Description unavailable

Strong molecular bonding formed by Ge 4s and O 2p orbitals contributes to a robust and endurable metal–oxygen framework of the spinel oxide structure, which is not achievable via common 3d–2p orbital hybridization alone, making the oxide cathodes exhibit extraordinarily stable electrochemical performance in lithium-ion batteries.

Photocatalysis | Hot Paper

Photocatalytic Chemical Crosslinking for Profiling RNA–Protein Interactions in Living Cells

  • First Published: 22 April 2022
Description unavailable

The dynamic interactions between RNA and proteins play crucial roles in regulating diverse cellular processes. Proteome-wide characterization of these interactions in their native cellular context remains desirable but challenging. A photocatalytic crosslinking (PhotoCAX) strategy for studying the composition and dynamics of protein–RNA interactions via mass spectrometry (PhotoCAX-MS) as well as RNA sequencing (PhotoCAX-seq) is reported.

Mechanochemistry | Very Important Paper

Reticular Synthesis of Hydrogen-Bonded Organic Frameworks and Their Derivatives via Mechanochemistry

  • First Published: 22 April 2022
Description unavailable

Efficient and green mechanochemistry was performed to realize the reticular synthesis of hydrogen-bonded organic frameworks with predictable structures. Moreover, a series of Pd@HOF composites were generated by the one-pot mechanosynthesis, which showed different catalytic activities for CO oxidation. The synergetic effect between Pd and HOF was revealed by in situ DRIFTS, proving the application potential of functionalized HOF-composites.

Organic Electronics | Hot Paper

Open Access

Modular Nitrogen-Doped Concave Polycyclic Aromatic Hydrocarbons for High-Performance Organic Light-Emitting Diodes with Tunable Emission Mechanisms

  • First Published: 29 March 2022
Description unavailable

Curved and fully conjugated N-pyrrolic polycyclic aromatic hydrocarbons (N-PAHs) were utilized as efficient emitters in thermally activated delayed fluorescence organic light-emitting diode (TADF/OLED) devices. The curvature increases the spatial separation between the highest occupied and lowest unoccupied molecular orbitals, leading to low singlet–triplet gaps, which are essential for high reverse intersystem crossing rates. The overall photoluminescence quantum yield (PLQY) is up to 86 %.

Upconversion | Hot Paper

Open Access

Efficient Triplet-Triplet Annihilation Upconversion Sensitized by a Chromium(III) Complex via an Underexplored Energy Transfer Mechanism

  • First Published: 28 March 2022
Description unavailable

The molecular ruby [Cr(bpmp)2]3+ with an earth-abundant chromium(III) central ion sensitizes green-to-blue triplet-triplet annihilation upconversion with 9,10-diphenylanthracene as the annihilator. The process involves a near-unity energy transfer efficiency via an underexplored reaction pathway, an anti-Stokes shift of 0.54 eV, and a maximum upconversion quantum yield of 12.0 %.

Quantum Dots

Minimizing the Reorganization Energy of Cobalt Redox Mediators Maximizes Charge Transfer Rates from Quantum Dots

  • First Published: 27 April 2022
Description unavailable

Choosing a redox-mediator with low reorganization energy vastly improves charge transfer rates from quantum dots by orders of magnitude.

Deuterium Labelling | Hot Paper

Open Access

Manganese-Catalysed Deuterium Labelling of Anilines and Electron-Rich (Hetero)Arenes

  • First Published: 29 April 2022
Description unavailable

A manganese biopolymer-supported catalyst is reported for hydrogen/deuterium exchange in anilines, phenols, heterocycles, and electron-rich arenes. Notably, taking advantage of deuterium oxide as easy-to-handle isotope source, deuterated compounds are obtained in high yields in a practical manner.

Separation Membranes

Open Access

Poly(ionic liquid)-Armored MXene Membrane: Interlayer Engineering for Facilitated Water Transport

  • First Published: 03 May 2022
Description unavailable

The surface hydrophilicity of nanochannels within 2D MXene-based membranes was readily engineered by poly(ionic liquid)s (PILs) as tailor-made modifier to assemble MXene laminates via electrostatic and surpamolecular interactions. By judicious choice of exchangeable counter anion of the PILs, the interlayer galleries were precisely altered in a wide hydrophilic-to-hydrophobic range to amplify the nanofiltration performance.

Theranostics

Multimodal Imaging-Guided Photothermal Immunotherapy Based on a Versatile NIR-II Aggregation-Induced Emission Luminogen

  • First Published: 28 March 2022
Description unavailable

A versatile NIR-II AIE luminogen displaying fluorescence, photoacoustic, and photothermal imaging functions was designed by using a benzo[c]thiophene moiety as a building block. This luminogen, when applied with an integrated programmed death-ligand 1 (αPD-L1) antibody, exhibits unprecedented performance in multimodal imaging-guided photothermal immunotherapy towards breast tumors.

Photoswitches

Multicolor Zinc(II)-Coordinated Hydrazone-Based Bistable Photoswitches for Rewritable Transparent Luminescent Labels

  • First Published: 23 April 2022
Description unavailable

Two hydrazone-based photoswitches with high emission quantum yields, excellent reversible photoisomerization properties, and long thermal stability are reported. Impressively, multiple emission colors can be obtained readily for these two photoswitches upon coordination with various zinc salts. Furthermore, the photo-controlled rewritable printing of invisible multicolor images with extremely high resolution and stability is achieved.

C-H Functionalization | Hot Paper

Open Access

Amine-Catalyzed Copper-Mediated C−H Sulfonylation of Benzaldehydes via a Transient Imine Directing Group

  • First Published: 20 April 2022
Description unavailable

Transient C−H sulfonylation of benzaldehydes is achieved using copper and catalytic β-alanine to form a directing group in situ. Aldehydes and sulfinate salts are coupled in a single step in high yields. Kinetic and mechanistic investigations are presented, with insights to the C−H activation step.

Nitrogen Reduction

Lattice-Confined Single-Atom Fe1Sx on Mesoporous TiO2 for Boosting Ambient Electrocatalytic N2 Reduction Reaction

  • First Published: 12 April 2022
Description unavailable

S-coordinated Fe single-atom catalysts on mesoporous TiO2 have been constructed by a universal lattice-confined strategy. This catalyst shows a unique nanoconfinement effect for the mass transfer and maximizes the active sites to mimic nitrogenase for ambient electrocatalytic N2 reduction reaction.

CO2 Methanation

Highly Selective Photocatalytic CO2 Methanation with Water Vapor on Single-Atom Platinum-Decorated Defective Carbon Nitride

  • First Published: 27 April 2022
Description unavailable

Atomically active sites are designed for CO2 methanation with water by integrating defective polymeric carbon nitride with single Pt atoms. Single Pt sites, carbon nitride defects and −OH groups synergistically work for different functions to achieve high activity and selectivity for CH4 production in photocatalytic CO2 reduction.

Supramolecular Chemistry

Metallo-Supramolecular Octahedral Cages with Three Types of Chirality towards Spontaneous Resolution

  • First Published: 27 April 2022
Description unavailable

Chiral metallo-supramolecular octahedral cages were obtained as conglomerates with spontaneous resolution. During crystallization, anions play a critical role in formation of racemic compounds or conglomerates. Moreover, the enantiopure cages are very stable in solution, and exhibit slow racemization even at extremely low concentrations.

Fluorescent Probes | Hot Paper

An Activatable Polymeric Nanoprobe for Fluorescence and Photoacoustic Imaging of Tumor-Associated Neutrophils in Cancer Immunotherapy

  • First Published: 06 April 2022
Description unavailable

An activatable polymeric nanoprobe (SPCy) is synthesized for near-infrared fluorescence (NIRF) and photoacoustic (PA) detection of neutrophil elastase (NE), a biomarker of tumor-associated neutrophils (TANs). SPCy reacts with NE in tumors to only turn on the NIRF and PA signals of hemicyanine but not the reference polymer backbone, leading to ratiometric NIRF and increased PA signals of TANs during cancer immunotherapy.

Lithium–Sulfur Batteries

Pushing Lithium–Sulfur Batteries towards Practical Working Conditions through a Cathode–Electrolyte Synergy

  • First Published: 24 April 2022
Description unavailable

The synergy of cathode engineering and electrolyte manipulation effectively enhance redox kinetics and cycling stability of Li−S batteries. This strategy is demonstrated to be effective in achieving high performance under wide temperature situations and enabling a stable Li−S pouch cell under a thin Li-metal anode, thick S cathode, and lean electrolyte conditions.

C−H Activation

Iridium-Catalyzed Ligand-Controlled Remote para-Selective C−H Activation and Borylation of Twisted Aromatic Amides

  • First Published: 20 April 2022
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A highly para-selective C−H borylation of aromatic amides is reported. The para borylation proceeds via an unprecedented substrate–ligand distortion between the twisted aromatic amides and a newly designed ligand framework (defa), which is different from the standard borylation ligand. A new type of catalytic system was developed by using this defa ligand that demonstrated excellent levels of para selectivity for a range of aromatic amides.

Supercapacitors

Interfacial Polymetallic Oxides and Hierarchical Porous Core–Shell Fibres for High Energy-Density Electrochemical Supercapacitors

  • First Published: 15 April 2022
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Hetero-structured polymetallic oxides/porous graphene core–sheath fibres are demonstrated as high-performance electrochemical supercapacitor electrodes via a microchannel self-assembly method. Because of rich micro-/mesoporous ionic pathways, a large accessible surface, high Faradaic activity and excellent interface electron conduction, the supercapacitors display remarkable areal capacitance, energy-density, long-life cycles and actual applications.

Asymmetric Catalysis

Catalytic Regio- and Enantioselective Protonation for the Synthesis of Chiral Allenes: Synergistic Effect of the Counterion and Water

  • First Published: 02 May 2022
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Pudovik addition/[1,2]-phospha-Brook rearrangement mediated by a chiral ScIII/N,N′-dioxide complex led to axially chiral trisubstituted allenes with a diarylphosphinate moiety. A synergistic effect of the counterion and water enabled regio- and enantioselective protonation after [1,2]-phospha-Brook rearrangement. Intramolecular dearomatization of N-Ph-substituted products gave bridged polycyclic architectures through stereospecific Himbert reaction.

Cancer Theranostics | Very Important Paper

A Hybrid Supramolecular Polymeric Nanomedicine for Cascade-Amplified Synergetic Cancer Therapy

  • First Published: 05 April 2022
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A hybrid supramolecular polymeric nanomedicine for cascade-amplified synergetic chemodynamic therapy and chemotherapy is constructed based on β-cyclodextrin/camptothecin host−guest molecular recognition and iron-carboxylate coordination. In synergy with a checkpoint blockade, this supramolecular nanomedicine leads to an enhanced therapeutic performance and long-term tumor remission.

Selective Alcohol Oxidation

Synergy in Au−CuO Janus Structure for Catalytic Isopropanol Oxidative Dehydrogenation to Acetone

  • First Published: 13 April 2022
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A unique Au−CuO Janus structure with a 0.5 nm ultrathin CuO layer was developed. The Au−CuO interfacial structure was confirmed to be extremely efficient for C−H activation; a dramatic decrease of the β-C−H bond scission energy barrier from 1.44 to 0.01 eV due to the strong affinity between the O of CuO and H of isopropanol, compared with Au sites alone, was observed.

Metals in Medicine | Very Important Paper

A New Strategy to Fight Metallodrug Resistance: Mitochondria-Relevant Treatment through Mitophagy to Inhibit Metabolic Adaptations of Cancer Cells

  • First Published: 05 April 2022
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A new strategy to fight metallodrug resistance through mitochondria-relevant treatment is reported. The cyclometalated IrIII complex Ir-Rhein could inhibit the metabolic adaptation of cancer cells by inducing severe mitochondrial damage and dysfunction. Moreover, complex Ir-Rhein could overcome metallodrug resistance through the regulation of the platinum resistance-related transporters.

Hydrogen Evolution Reaction | Hot Paper

Open Access

MXene Analogue: A 2D Nitridene Solid Solution for High-Rate Hydrogen Production

  • First Published: 19 April 2022
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A new MXene analogue, V-Mo-based 2D layered transition metal nitride solid solution (V0.2Mo0.8N1.2), was synthesized via a catalytic molten-salt method. It exhibited excellent activity and stability for hydrogen evolution reaction, superior to most MXenes. Boosted electrocatalytic performance originates from an optimized electronic structure induced by V atom alloying.

Supramolecular Polymers | Very Important Paper

Hydrogen-Bonded Supramolecular Polymer Adhesives: Straightforward Synthesis and Strong Substrate Interaction

  • First Published: 15 April 2022
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A straightforward synthetic strategy towards strong supramolecular adhesives is reported, based on a side-chain barbiturate (Ba) and Hamilton wedge (HW) functionalized polymer. Specific Ba/HW interactions serve as cohesive domains to maintain polymeric network integrity, while molecular configuration of individual Ba or HW moieties linked onto substrates via diverse H-bonding interactions, form adhesive domains and endow strong adherence.

Silicon Chemistry

Open Access

Synthesis and Characterization of Hypercoordinated Silicon Anions: Catching Intermediates of Lewis Base Catalysis

  • First Published: 19 April 2022
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The Lewis superacid bis(perchlorocatecholato)silane serves as a binding platform for weak anionic donors, providing the first characterized anionic bromido, iodido, formato, acetato, triflato, and sulfato silicates. This set allows to evaluate the structural and electronic perturbation of silicon species and substantiates their role in Lewis base catalysis.

Solar Cells | Hot Paper

Triarylamine/Bithiophene Copolymer with Enhanced Quinoidal Character as Hole-Transporting Material for Perovskite Solar Cells

  • First Published: 11 April 2022
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Triarylamine/bithiophene copolymers (TABT), synthesized via iron-catalyzed C−H/C−H coupling, have been applied as hole-transporting materials for perovskite solar cells (PVSCs). Owing to the film uniformity, enhanced quinoidal conjugation in radical cation state, and excellent ionization potential matching, a PVSC using a mesityl substituted TABT polymer outperformed devices using reference standards such as PTAA and Spiro-OMeTAD.

Mesoporous Carbon

Liquid Na/K Alloy Interfacial Synthesis of Functional Porous Carbon at Ambient Temperature

  • First Published: 26 April 2022
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Porous carbons were directly synthesized under ambient temperature via a liquid metal interfacial engineering strategy. Unlike the traditional carbons, these materials are abundant with active sites of C−Cl bonds. Imidazole and 1,2-dibromoethane were tandem-grafted on this porous carbon. Amine and bromide ion showed a synergistic effect to promote the catalytic reaction for cycloaddition of CO2, resulting in excellent catalytic performance.

Perovskites | Hot Paper

Avoiding Structural Collapse to Reduce Lead Leakage in Perovskite Photovoltaics

  • First Published: 12 April 2022
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Crystal structural collapse in perovskite films governs the Pb leakage after exposure to water as indicated by Noyes-Whitney Model simulation. It is effectively retarded by constructing a chemically stable Dion-Jacobson two-dimensional (2D) perovskite (DOE)PbI4−xClx at the surface of the film.

Photoluminescence

Highly Fluorescent Bipyrrole-Based Tetra-BF2 Flag-Hinge Chromophores: Achieving Multicolor and Circularly Polarized Luminescence

  • First Published: 05 May 2022
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A series of tetra-BF2 complexes with 2,2′-bipyrrole ligands that emit in the visible to red region in solution and in the solid state were synthesized by a one-pot reaction. The dyes are rigid but can rotate flexibly around the bipyrrole moiety, resulting in large Stokes shifts and high quantum yields. Tuning the rotational barrier enables circularly polarized emission based on axial chirality to be achieved.

Microfluidic Synthesis

Fibrous Nanoreactors from Microfluidic Blow Spinning for Mass Production of Highly Stable Ligand-Free Perovskite Quantum Dots

  • First Published: 14 April 2022
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Fiber-spinning chemistry based on a microfluidic blow spinning (MBS) technique is developed to construct fibrous nanoreactors allowing mass production of ligand-free perovskite quantum dots (PQDs). The resultant PQDs/polymer nanofiber films possess high fluorescence stability under extreme conditions like light irradiation, heating and water dipping, which show potential applications in photocatalytic CO2 reduction and optoelectronic devices.

Zeolite Catalysts | Hot Paper

Open Access

Thermal Alteration in Adsorption Sites over SAPO-34 Zeolite

  • First Published: 26 April 2022
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To better identify the structure of the active sites in zeolites under real reaction conditions, we demonstrate that the adsorption mode of acetone over classical Brønsted acid sites (BAS) can be thermally converted into the induced Frustrated Lewis Pair (FLP) adsorption mode in SAPO-34 zeolite.

Synthetic Methods | Hot Paper

Metal-Free SF6 Activation: A New SF5-Based Reagent Enables Deoxyfluorination and Pentafluorosulfanylation Reactions

  • First Published: 26 April 2022
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A new reagent has been designed through 2-electron activation of SF6 with commercially available tetrakis(dimethylamino)ethylene (TDAE) under blue LED irradiation. The versatility of this new SF5-based reagent has been demonstrated for the deoxyfluorination of CO2 and the fluorinative desulfurization of CS2 affording useful fluorinated amines. Moreover, SF5Cl could be generated under mild conditions from reagent I allowing chloro-pentafluorosulfanylation of alkenes and alkynes.

Nitrogen Heterocycles

Open Access

Evolution of the Dearomative Functionalization of Activated Quinolines and Isoquinolines: Expansion of the Electrophile Scope

  • First Published: 13 May 2022
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Reductive functionalisation of quinolinium and isoquinolinium salts with formic acid as the terminal reductant was possible under transition-metal-free conditions or rhodium catalysis with very low catalyst loadings. A wide range of electrophiles, including enones, imides, unsaturated esters and sulfones, β-nitrostyrenes and aldehydes, were intercepted by the enamine species formed in situ to generate substituted tetrahydro(iso)quinolines.

Carbocycles

Beyond Bioisosteres: Divergent Synthesis of Azabicyclohexanes and Cyclobutenyl Amines from Bicyclobutanes

  • First Published: 20 April 2022
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By exploiting the divergent reactivity of bicyclobutanes undergoing addition to imines, highly-functionalized and stereochemically-defined azabicyclohexanes and cyclobutenyl amines are easily accessible. These modular syntheses provide new and selective methods to prepare Csp3-rich scaffolds with potential beyond bioisosteric replacements in medicinal chemistry.

Photoacids | Hot Paper

Open Access

Electronic Structure Changes of an Aromatic Amine Photoacid along the Förster Cycle

  • First Published: 24 March 2022
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Electronic structural changes along the Förster cycle of an aromatic amine photoacid are monitored with time-resolved nitrogen K-edge spectroscopy, providing key insight into the factors responsible for the photoacidity properties.