Angewandte Chemie

An exposed Au atom on Au(111) in Au₅₂ nanoclusters and as-formed surface/interface environment were constructed by introducing nonaromatic ligand. In situ characterizations and simulations confirmed the activation of CO₂ and the accelerated protonation of strongly hydrogen-bonded water by the surface/interface modification, leading to pH-universal electrocatalysis with high activity, selectivity, and durability.

Cyclic boronic hemiesters, boron isosteres of lactones, display unique and valuable chemical properties. Herein, we report a novel method for their synthesis via nickel-catalyzed decarbonylative borylation, enabled by electron-rich phosphine ligands to achieve a formal “C-to-B” atom swap. This strategy efficiently transforms a variety of coumarin derivatives and seven-membered dibenzolactones into the corresponding benzoxaborines, showcasing broad functional group tolerance and synthetic versatility.

Triphenylchlorosilane (Ph₃SiCl) was developed as a tetrachlorosilane surrogate for the iterative and controllable ligation of four different alcohols to one silicon center to generate fully heteroleptic tetraalkoxysilanes. Mechanistic studies revealed the unusual transformations of Wheland intermediates into both silicon cations and silylated phenylhalonium ions in low and comparable activation barriers.

Crystal engineering and facet engineering were concurrently employed to develop a series of precious-metal-free heterobimetallic MOFs (M-BCA-M', M = Cu⁺, M' = Zr⁴⁺ or Hf⁴⁺) for record-high photocatalytic hydrogen production in pristine MOFs. The high performance and crystal-facet dependent behaviors were investigated to provide molecular-level insights into the coordination regulation and morphology control of pristine MOFs for efficient photocatalysis.

Fully exposed silver clusters were successfully anchored on poly(heptazinimide), demonstrating exceptional photocatalytic activity toward H₂O₂ generation in pure water from O₂. Systematic evaluation revealed that it also exhibited significantly enhanced performance compared to their single-atom counterpart due to superior electronic properties and synergetic effect between adjacent Ag atoms.

The hierarchical pore channels of MIL-100 confine LiI to form a conductive ionic network, while its triple-level cross-linked multi-stage porous restricts TFSI⁻ anion mobility, enabling rapid Li⁺ transport and uniform deposition by optimizing ion flux and suppressing space charge effects.

Highly efficient ultra-deep-blue TADF emitters were developed through the construction of multipathway charge transfer characteristics. OLEDs employing the optimized molecule as the terminal emitter and as a sensitizer exhibit high-performance deep-blue electroluminescence, achieving EQEs of up to 24.7% and 37.9%, with corresponding CIE-y values of 0.038 and 0.106, respectively.

The photoluminescence quantum yield (PLQY) of one-dimensional (CH₃)₄NMnCl₃ (TMMC) doped with Cd²⁺ remains consistently high (∼95%) across the studied composition range (x = Cd_x/Mn_1-x = 0–0.22). By combining PL lifetime measurements, high-pressure optical absorption spectroscopy, and X-ray diffraction structural analysis, we demonstrate that the PLQY exhibits only minimal dependence on x. This finding contrasts with recent reports,¹ claiming that the PLQY initially rises with Cd²⁺ content up to x = 0.08, then declines sharply from 95% to 77% at x = 0.22.

Channel confinement via rigid cylindrical pillaring in a MOF framework enables molecular sieving through elliptical windows, offering a blueprint for ambient-condition xylene isomer separation.