Angewandte Chemie International Edition

Nickel-catalyzed transannulation reactions triggered by the extrusion of small gaseous molecules have emerged as a powerful strategy for the efficient construction of heterocyclic compounds. However, it’s asymmetric synthesis remains challenging because of the difficulty in controlling stereo- and regioselectivity. Herein, we report the first nickel-catalyzed asymmetric synthesis of N–N atropisomers by the denitrogenative transannulation of benzotriazones with internal alkynes. A broad range of N–N atropisomers was obtained with excellent regio- and enantioselectivity under mild conditions. Moreover, density functional theory (DFT) calculations provided insights into the nickel-catalyzed reaction mechanism and enantioselectivity control.

Published in: "Angewandte Chemie International Edition".

Assemblies of nanoparticles at liquid interfaces hold promise as dynamic “active” systems when there are convenient methods to drive the system out of equilibrium via crowding. To this end, we show that oversaturated assemblies of charged nanoparticles can be realized and held in that state with an external electric field. Upon removal of the field, strong interparticle repulsive forces cause a high in-plane electrostatic pressure that is released in an explosive emulsification. We quantify the packing of the assembly as it is driven into the oversaturated state under an applied electric field. Physiochemical conditions substantially affect the intensity of the induced explosive emulsification, underscoring the crucial role of interparticle electrostatic repulsion.

Published in: "Angewandte Chemie International Edition".

Metal-organic framework (MOF)-based mixed matrix membranes (MMMs) have shown great promises to overcome the performance upper limit of polymeric membranes for various gas separation processes. However, the gas separation properties of the MMMs largely depend on the MOF-polymer interfacial compatibility which is a metric difficult to quantify. In most cases, whether a MOF filler and a polymer matrix make a good pair is not revealed until the gas transport experiments are performed. This is because there is a lack of characterization techniques to directly probe the MOF-polymer interfacial compatibility. In this work, we demonstrate a self-sorting method to rank the interface compatibility among several MOF-polymer pairs. By mixing one MOF with two polymers in an MMM, the demixing of two polymers will form two polymer domains. The MOF particles will preferably partition into the “preferred” polymer domain due to their higher interfacial affinity. By scanning different polymer pairs, a rank of MOF-polymer interfacial compatibility from high to low can be obtained. Moreover, based on this ranking, it was also found that a highly compatible MOF-polymer pair suggested by this method also corresponds to a more predictable MMM gas separation performance.

Published in: "Angewandte Chemie International Edition".

Developing highly stable porous coordination polymers (PCPs) with integrated electrical conductivity is crucial for advancing our understanding of electrocatalytic mechanisms and the structure-activity relationship of electrocatalysts. However, achieving this goal remains a formidable challenge because of the electrochemical instability observed in most PCPs. Herein, we develop a “modular design” strategy to construct electrochemically stable semiconducting PCP, namely, Fe-pyNDI, which incorporates a chain-type Fe-pyrazole metal cluster and π-stacking column with effective synergistic effects. The three-dimensional electron diffraction (3D ED) technique resolves the precise structure. Both theoretical and experimental investigation confirms that the π-stacking column in Fe-pyNDI can provide an efficient electron transport path and enhance the structural stability of the material. As a result, Fe-pyNDI can serve as an efficient model electrocatalyst for nitrate reduction reaction (NO3RR) to ammonia with a superior ammonia yield of 339.2 μmol h-1 cm-2 (14677 μg h−1 mgcat.−1) and a faradaic efficiency of 87 % at neutral electrolyte, which is comparable to state-of-the-art electrocatalysts. The in-situ X-ray absorption spectroscopy (XAS) reveals that during the reaction, the structure of Fe-pyNDI can be kept, while part of the Fe3+ in Fe-pyNDI was reduced in situ to Fe2+, which serves as the potential active species for NO3RR.

Published in: "Angewandte Chemie International Edition".

Developing recyclable heterogeneous catalysts for organic synthesis requires a deep understanding of active site architectures during surface-catalyzed reactions. Our approach, combining in-situ X-ray absorption spectroscopy and droplet-based microfluidics, investigates Suzuki–Miyaura coupling over palladium single-atoms on carbon nitride. The results highlight the need for distinct design criteria compared to traditional homogeneously catalyzed processes. Abstract Single-atom heterogeneous catalysts (SACs) hold promise as sustainable alternatives to metal complexes in organic transformations. However, their working structure and dynamics remain poorly understood, hindering advances in their design. Exploiting the unique features of droplet-based microfluidics, we present the first in-situ assessment of a palladium SAC based on exfoliated carbon nitride in Suzuki–Miyaura cross-coupling using X-ray absorption spectroscopy. Our results confirm a surface-catalyzed mechanism, revealing the distinct electronic structure of active Pd centers compared to homogeneous systems, and providing insights into the stabilizing role of ligands and bases. This study establishes a valuable framework for advancing mechanistic understanding of organic syntheses catalyzed by SACs.

Published in: "Angewandte Chemie International Edition".

This Minireview summarizes recent advances in the growing field of the applied supramolecular chemistry of the sumanene buckybowl, highlighting the major fields in which potential or real applications of sumanene have been demonstrated. Special attention is paid to sumanene-tethered functional supramolecular materials and architectures and ion-selective molecular receptors. Possible future trends in this emerging area are also discussed. Abstract Sumanene is a buckybowl molecule that is continuously attracting the attention of the scientific community because of its unique geometrical and physicochemical properties. This Minireview systematically summarizes advances and considerations regarding the applied supramolecular chemistry of sumanene. This work highlights the major fields in which potential or real applications of sumanene molecule have been reported to date, such as the design of sumanene-containing functional supramolecular materials and architectures, sumanene-based drug-delivery systems, or sumanene-tethered ion-selective molecular receptors. An assessment of the current status in the applied supramolecular chemistry of sumanene is provided, together with an emphasis on the key advances being made. Discussion on those milestones that are still to be achieved within this emerging field is also provided.

Published in: "Angewandte Chemie International Edition".

Carotenoids tend to form supramolecular aggregates via non-covalent interactions where the chirality of individual molecules is amplified to the macroscopic level. We show that this can also be achieved for non-chiral carotenoid monomers interacting with polysaccharides. The chirality induction in canthaxanthin (CAX), caused by heparin (HP) and hyaluronic acid (HA), was monitored by chiroptical spectroscopy. Electronic circular dichroism (ECD) and Raman optical activity (ROA) spectra indicated the presence of multiple carotenoid formations, such as H- and J-type aggregates. This is consistent with molecular dynamics (MD) and density functional theory (DFT) simulations of the supramolecular structures and their spectroscopic response.

Published in: "Angewandte Chemie International Edition".