Fluorination from Surface to Bulk Stabilizing High Nickel Cathode Materials with Outstanding Electrochemical Performance.

High nickel layered oxides provide high energy densities as cathodes for next-generation batteries. However, critical issues such as capacity fading and voltage decay, which derive from labile surface reactivity and phase transition, especially under high-rate high-voltage conditions, prevent their commercialization. Here we propose a fluorination strategy to simultaneously introduce F atoms into oxygen layer and create a F aggregated interface.

Lucas Foppa.

"A key experience in my education was the double-degree exchange program that I did during my BSc. Experiencing different perspectives of education and culture in Brazil and France expanded my horizons permanently… Guaranteed to make me laugh is a good surrealist movie…" Find out more about Lucas Foppa in his Introducing… Profile.

Benzyl Ammonium Carbamates Undergo Two-Step Linker Cleavage and Improve the Properties of Antibody Conjugates.

Targeted payload delivery strategies, such as antibody-drug conjugates (ADCs), have emerged as important therapeutics. Although considerable efforts have been made in the areas of antibody engineering and labeling methodology, improving the overall physicochemical properties of the linker/payload combination remains an important challenge. Here we report an approach to create an intrinsically hydrophilic linker domain.

Jordan Hobbs.

"I would have liked to have discovered one of the early room temperature liquid crystal mixtures. Probably a good bit of money in those patents!… My science 'hero' is Alan Turing. For everything he accomplished whilst also being an LGBTQ+ icon…" Find out more about Jordan Hobbs in their Introducing… Profile.

Angewandte Chemie: One Journal, Many Faces.

The authors of this Editorial now lead Angewandte Chemie and its editorial team as Editors-in-Chief and will continue to collaborate closely with the German Chemical Society as well as the journal's Scientific Advisory Committee and International Advisory Board in shaping the journal.

Self-Immolative Polymers Derived from Renewable Resources via Thiol-Ene Chemistry.

The development of polymers from renewable resources is a promising approach to reduce reliance on petrochemicals. In addition, depolymerization is attracting significant attention for the breakdown of polymers at their end-of-life or to achieve specific stimuli-responsive functions. However, the design of polymers incorporating both of these features remains a challenge.

Linker Installation in a Metal-Organic Framework for Enhanced Quantitative Redox Species Recognition.

Linker installation has proven to be an effective strategy for introducing diverse functional groups into metal-organic frameworks (MOFs). Reductants and oxidants are found in various environments, but their accumulation poses a danger due to their high reactivity, necessitating prompt monitoring instantly, particularly in natural environments and industrial processes. In this study, a series of redox-active dyes were successfully incorporated into a flexible Zr-based MOF, PCN-700, through linker installation strategy.

Cleavage and Reassembly of 1,3-Dicarbonyls with Enaminones To Synthesize Highly Functionalized Naphthols.

The cleavage of carbon-carbon bonds and their subsequent reassembly into highly functionalized and useful molecules in an atom-efficient manner has always been a central focus in the realm of organic synthesis. In this report, we describe the construction of highly functionalized naphthol esters via a tandem reassembly process, driven by Ullmann-type coupling of enaminones and 1,3-dicarbonyl compounds. Mechanistic investigations suggest the involvement of C(sp²)-C(sp³) coupling, cyclization, two acyl migrations, aromatization, and additional transformations within this tandem sequence.

Cooperative Multiscale-Assembly for Directional and Hierarchical Growth of Highly Oriented Porous Organic Cage Single-Crystal Microtubes and Arrays.

The directional assembly of porous organic molecules into long-range ordered architectures, featuring controlled hierarchical porosity and oriented pore channels with defined spatial arrangements, is a fundamental challenge in chemistry and materials science. Herein, using porous organic cages as starting units, we present a cooperative multiscale-assembly strategy enabling the simultaneous alignment of pore channels and directional hierarchical growth in a single step. At the microscopic level, we employed double solvents to manipulate the intermolecular packing of microporous tetrahedral [4+6] imine cages (CC1 and CC3), resulting in pore channel orientation.

Program-Modulated Kinetics of Perovskite-Film Growth by Molecular "Thruster" for High-Efficiency and Stable Perovskite Solar Cells.

The rapid reaction between lead iodide (PbI2) and formamidinium iodide (FAI) complicates the fabrication of high-quality formamidinium lead iodide (FAPbI3) films. Conventional methods, such as using nonvolatile small molecular additives to slow the reaction, often result in buried interfacial voids and molecule diffusion, compromising the devices' operational stability. In this study, we introduced a molecular "thruster"-a hypervalent iodine (III) compound with three carbonyl groups and a C--I⁺ bond-that possesses coordination and dissociation abilities, enabling programed modulation of perovskite-film growth kinetics.

Hydroalkylation of Vinylarenes by Transition-Metal-Free In Situ Generation of Benzylic Nucleophiles Using Tetramethyldisiloxane and Potassium tert-Butoxide.

Hydrosilanes and Lewis bases are known to promote various reductive defunctionalizations, rearrangements, and silylation reactions, facilitated by enigmatic silicon/Lewis base-derived reactive intermediates. Despite the wide variety of transformations enabled by this reagent combination, no examples of intermolecular C(sp3)-C(sp3) forming reactions have been reported. In this work, we've identified 1,1,3,3-tetramethyldisiloxane (TMDSO) and KOtBu as a unique reagent combination capable of generating benzylic nucleophiles in-situ from styrene derivatives, which can subsequently react with alkyl halides to give a new C(sp3)-C(sp3) linkage via formal hydroalkylation.

Chemocatalytic Conversion of Dinitrogen to Ammonia Mediated by a Tungsten Complex.

Whereas molybdenum dinitrogen complexes have played a major role as catalytic model systems of nitrogenase, corresponding tungsten complexes were in most cases found to be catalytically inactive. Herein, we present a modified pentadentate tetrapodal (pentaPod) phosphine ligand in which two dimethylphosphine groups of the pentaPodMe (P5Me) ligand have been replaced with phospholanes (Pln). The derived molybdenum complex [Mo(N2)P5Pln] generates 22 and the analogous tungsten complex [W(N2)P5Pln] 7 equivalents of NH3 from N2 in the presence of 180 equiv.

In-situ Constructed Core-shell Catalyst Enabling Subzero Capacity Unlocking of Cost-effective and Long-life Vanadium Flow Batteries.

Vanadium flow battery (VFB) promises a route for achieving grid-scale power storage by harnessing renewable energy sources. However, the sluggish reaction kinetics of vanadium redox couples and serious hydrogen evolution reaction (HER) still restrict the further development of VFB. Addressing these challenges requires not only effective solutions but also ones that are cost-efficient and scalable to meet the demands of affordable energy storage.

Fluoromethyl Triflate and Fluoromethyl Fluorosulfonate: Easily Accessible and Powerful Fluoromethylation Reagents.

Fluoromethyl triflate (superfluoromethyl, SFM, FCH2OSO2CF3) and fluoromethyl fluorosulfonate (magic fluoromethyl, MFM, FCH2OSO2F) are two easily synthesized, highly effective and non-ozone depleting fluoromethylation reagents. They are analogous to the well-known and widely used methylation re-agents CH3OSO2CF3 and CH3OSO2F. Both SFM and MFM have been fully characterized by multinuclear NMR spectroscopy (1H, 13C, 17O, 19F, 33S).

Engineering of HO-Zn-N2 Active Sites in Zeolitic Imidazolate Frameworks for Enhanced (Photo)Electrocatalytic Hydrogen Evolution.

Currently, lack of ways to engineer specific and well-defined active sites in zeolitic imidazolate frameworks (ZIFs) limits our fundamental knowledge with respect to the mechanistic details for (photo)electrocatalytic hydrogen evolution reaction (HER). Here, we introduce the open metal sites into ZIFs through the selective ligand removal (SeLiRe) strategy, comprehensively characterize the altered structural and electronic features, and evaluate their role in HER. In-situ electrochemical analysis and X-ray absorption spectroscopy reveal the formation of high-valence HO-Zn-N2 sites through the binding of Zn-N2 with electrolyte hydroxide.

High-Valent Cobalt-Difluoride in Oxidative Fluorination of Saturated Hydrocarbons.

The heme paradigm where Fe=O acts as the C-H oxidant and Fe-OH rebounds with the formed carbon-centered radical guides the design of the prototypical synthetic hydroxylation catalyst. We are exploring methods to evolve beyond the metal-oxo oxidant and hydroxide rebound, to incorporate a wider array of functional group. We have demonstrated the application of CoII(OTf)2 (10 mol% catalyst; OTf = trimfluoromethanesulfonate) in combination with polydentate N-donor ligands (e.

Mechanistic Insights Into Post-translational α-Keto-β-Amino Acid Formation by a Radical S-Adenosyl Methionine Peptide Splicease.

Radical S-adenosyl methionine enzymes catalyze a diverse repertoire of post-translational modifications in protein and peptide substrates. Among these, an exceptional and mechanistically obscure example is the installation of α-keto-β-amino acid residues by formal excision of a tyrosine-derived tyramine unit. The responsible spliceases are key maturases in a widespread family of natural products termed spliceotides that comprise potent protease inhibitors, with the installed β-residues being crucial for bioactivity.

Partially Interstitial Silicon-Implanted Ruthenium as an Efficient Electrocatalyst for Alkaline Hydrogen Evolution.

To enhance the alkaline hydrogen evolution reaction (HER), it is crucial, yet challenging, to fundamentally understand and rationally modulate potential catalytic sites. In this study, we confirm that despite calculating a low water dissociation energy barrier and an appropriate H adsorption free energy (ΔG*H) at Ru-top sites, metallic Ru exhibits a relatively inferior activity for the alkaline HER. This is primarily because the Ru-top sites, which are potential H adsorption sites, are recessive catalytic sites, compared with the adjacent Ru-hollow sites that have a strong ΔG*H.

Anionic Doping in Layered Transition Metal Chalcogenides for Robust Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) are among the most promising next-generation energy storage technologies. However, a slow Li-S reaction kinetics at the LSB cathode limit their energy and power densities. To address these challenges, this study introduces an anionic-doped transition metal chalcogenide as an effective catalyst to accelerate the Li-S reaction.

Solvent-Dependent Divergent Cyclization of Bicyclo[1.1.0]butanes.

Bicyclo[1.1.0]butanes (BCBs) have recently garnered significant research interest as versatile precursors for synthesizing potential [n.

Programmable Self-assembly from Two-dimensional Nanosheets to Spiral, Twisted and Branched Nanostructures.

Self-assembly of nanomaterials into hierarchical structure is of great interest to fabricate functional materials. However, programmable design of the assembled structures remains a great challenge. Herein, we reported a programmable self-assembly strategy to customize the assembled structure.

Porous Halogen-Bonded Frameworks Assembled through Hetero-polytopic Ion Pair Templation.

Halogen-bonding (XB) interactions have been extensively studied in the preparation of crystalline frameworks, yet porous 3D framework materials built on XBs remain elusive. The donor-acceptor interactions are strengthened by use of anionic XB acceptors; however, the requisite charge-balancing cations typically disrupt the framework and occupy potential void space. In this work, we prepare a tetratopic XB donor bearing a crown ether moiety for sodium cation sequestration.

Copper-Catalyzed Enantioselective Skeletal Editing through a Formal Nitrogen Insertion into Indoles to Synthesize Atropisomeric Aminoaryl Quinoxalines.

Skeletal editing represents an attractive strategy for adding complexity to a given molecular scaffold in chemical synthesis. Isodesmic reactions provide a complementary skeletal editing approach for the redistribution of chemical bonds in chemical synthesis. However, catalytic enantioselective isodesmic reaction is extremely scarce and enantioselective isodesmic reaction to synthesize atropisomeric compounds is unknown.

Boosting the Performance of Iridium Single Atom Catalyst in a Porous Organic Polymer for Glycerol Conversion to Lactic Acid.

Single-atom catalysts (SACs) inherit the merit of both homogeneous and heterogeneous systems with atomically dispersed mononuclear metal centers on the solid supports. Herein, we developed an Ir-SAC catalyst via the polymerization of an active homogeneous 2-picolinylhydrazone ligand-based iridium (Ir) metal complex. Such catalysts provide great stabilization against migration and agglomeration due to the strong covalent C-C bond linkage of active complexes and the polymer matrix.