Angewandte Chemie最新文献

A biomimetic NO capture-activation-conversion strategy was firstly formulated by encapsulating N-acetylcysteine (NAC) within a nicotinamide adenine dinucleotide (NADH) mimic-containing coordination capsule as reported by Liang Zhao and co-workers in the Communication (e19123). The platform echos the native S-nitrosoglutathione reductase and exhibits remarkable performance for NH₃ electrosynthesis, expanding a new horizon for existing nitrogen conversion methodologies.

A novel stereospecific, transition-metal-free alkylation of cyanohydrins with enantiomerically enriched secondary tosylates is described. This method enables the general, efficient, and operationally simple synthesis of enantioenriched α-tertiary ketones by leveraging the nucleophilicity of cyanohydrin anions, which serve as umpolung carbonyl equivalents to facilitate highly stereospecific S_N2 substitutions. Reactions involving alkenyl cyanohydrins proceed through a stereoconvergent olefin synthesis (SCOS) from a geometric E/Z mixture, furnishing stereochemically defined, conjugated α-tertiary ketones. This methodology exhibits broad functional group tolerance, accommodating unactivated and sterically hindered acyclic and cyclic secondary tosylates. The resulting chiral ketones are configurationally stable and can be readily converted into synthetically versatile intermediates using classical transformations. The utility of this approach is exemplified by a concise, stereospecific synthesis of (R)-cyclamen aldehyde, underscoring its potential to streamline the preparation of enantioenriched α-tertiary ketones—structural motifs that feature prominently in both natural and non-natural products and serve as key intermediates in target-directed synthesis.

In the Research Article (e202519101), Tengfei Yan, Ofer Reany, Junqiu Liu, and co-workers present a reversible, light-controlled ON/OFF chloride channel based on azobenzene-functionalized semiaza-bambus[6]urils. These biomimetic systems achieve stimulus-responsive chloride transport through photoisomerization, demonstrating unprecedented controllability in both liposomal membranes and living cells. The (E)-isomer selectively enables chloride flux, induces significant mitochondrial and lysosomal disruption, and promotes apoptosis in cancer cells, while the (Z)-isomer remains inactive.

Hochdrucksynthesen zwischen Antimon und molekularem Stickstoff in einer laserbeheizten Diamantstempelzelle führten zur Bildung von oC32-Sb₃N₅ (51(1) GPa) und mP20-Sb₂(N₈) (> 100 GPa). Beide Phasen wurden mittels Einkristall-Röntgenmikrodiffraktion identifiziert und durch Berechnungen mittels Dichtefunktionaltheorie vollständig bestätigt. mP20-Sb₂(N₈) ist das erste Oligonitrid, das bisher unbekannte, verdrehte und kovalent einfach gebundene (N₈)¹⁰⁻ Ketten enthält, deren charakteristische Schwingungen zusätzlich mittels Raman-Spektroskopie identifiziert wurden.

Die autonome Entdeckung von Reaktionen unter Verwendung der ab initio-Nanoreaktor-Molekulardynamik in Kombination mit periodischen DFT-Berechnungen erläutert die selektive katalytische Reduktion von NO zu $$ und Nebenreaktionen, bei denen $$ entsteht. Dies ermöglicht die autonome Entdeckung von Reaktionsmechanismen, einschließlich der Brønsted-Stellen und Protonentransporte, was zu einem komplexen chemischen Reaktionsnetzwerk führt. Die freien Energiebarrieren ausgewählter Reaktionspfade werden angegeben.

Establishing a congruent approach to delivering a pnictide atom (Pn³⁻ = P, As, and Sb) to transition metal ions is a challenge, especially for the heavier congeners As and Sb, and when varying the transition metal. We showcase here a convenient route to molecular forms of one coordinate stibide ligands bound to Zr^IV and Ti^IV ions, represented by the discrete salts [K(L)][(PN)₂M≡Sb] (M = Zr (2), Ti (10); PN⁻ = (N-(2-PⁱPr₂-4-methylphenyl)-2,4,6-Me₃C₆H₂; L = 2,2,2-Kryptofix or 18-C-6 crown-ether/2THF), which were prepared via H₂ extrusion from [K(18-C-6)(THF)SbH₂] added to the Zr^IV cyclometallated-hydride, [(PN)(PN’)Zr(H)] (1), and the Ti^II precursor [K(18-C-6)][(PN)₂TiCl] (8) respectively. This strategy was extended to the lighter congeners Pn = As, P using [K(18-C-6)(THF)AsH₂] (M = Zr (3)), and NaPH₂ (M = Ti (6)). Structural and computational studies were applied to understand the bonding trends in the pnictide series, and the role of the metal ion.

The temperature-controlled transformation of organic molecules at interfaces is an incipient yet powerful strategy for tailoring their structural and physico-chemical properties. In this study, we investigate the substrate- and thermal-selective reactions of bis(3,4-thiophene-fused)tetrabromo-p-benzoquinodimethane molecule (1), focusing on its behavior at distinct coinage metal interfaces, namely Au(111) and Ag(111). Combining scanning probe microscopy and theory, we demonstrate that its sequential transformations are highly dependent on the substrate material and the specific reaction temperatures. When a benzodithiophene precursor, endowed with = CBr₂ units, is deposited under ultra-high vacuum (UHV) conditions on both substrates held at room temperature (RT), or annealed to 100 °C in the case of Au(111), a self-assembly is formed comprising 1D covalent polymers achieved through debromination and homocoupling, which are aligned in a parallel fashion thanks to supramolecular interactions, giving rise to a 2D supramolecular polymer. However, when the substrate is held at or above 175 °C during deposition, the molecular precursors (1) undergo substrate-specific intramolecular reactions. On Au(111), a major transformation into pentalenodithiophene species is observed, concomitant with the formation of benzotrithiophene. On Ag(111), instead, pentalenodithiophene species are precluded. These findings highlight the importance of substrate selection and temperature control in enabling precise molecular transformations at the nanoscale.

The solution-based chemical prelithiation of electrode materials is an effective approach to elevate the initial coulombic efficiency (ICE) and energy-density of the Li-ion battery. Although various lithium-aromatic compound complex solutions (LACSs) have been reported as prelithiation reagents, fundamental understandings are still lacking regarding their drastic difference in prelithiation behavior. In this work, the rate-determining step and some key factors that affect the prelithiation capability were recognized via electrochemical evaluation, spectroscopic analysis, and density functional theory (DFT) calculations. Considering the inherent correlations between the potential of electrochemical Li⁺-extraction from LACS upon cyclic voltammetry (the oxidation potential of LACS, E_O), the calculated highest occupied molecular orbital (HOMO) energy level, the binding energy (BE) of the solvated Li-ions to the solution (BE_solution), and the prediction accuracy of prelithiation capability and calculations efficiency, we proposed BE-assisted E_O as a descriptor for its prelithiation feasibility. This strategy will provide important guidance for the rapid selection and rational design of LACSs for efficient chemical prelithiation.

This cover illustrates a near-infrared chiral nanotherapeutic (D-TeSe NPs) to brain tumor. It symbolizes a chirality-driven paradigm that uses near-infrared circularly polarized light to selectively amplify NPs-mediated oxidative stress in cancer cells to reactive oxygen species, offering a precise and potent treatment for brain diseases. More in the Research Article (e202516990), Gaoyang Wang, Feng Bai, Jiefei Wang, and co-workers.

In the Communication (e18517), André K. Eckhardt and co-workers demonstrate the advantageous properties of solid para-hydrogen (p-H₂) matrices for electron paramagnetic resonance spectroscopy by investigating the 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) radical and an in situ generated P-centered mono-radical. The spectral resolution of the P-centered radical in p-H₂ is roughly enhanced by a factor of three compared to argon.