Chemistry - A European Journal最新文献

Rings running around. In their Research Article (DOI: 10.1002/chem.202404731), A. Tsurusaki, K. Kamikawa and co-workers report how they synthesized new benzo-fused phosphepines and investigated the phosphepine ring inversion. These compounds are represented as mantas with the central phosphepine framework and a phenylethynyl group as the body and tail, respectively. The movement of the manta's fins also expresses the phosphepine ring inversion. Artwork by Norifumi Kosaka of YAP Inc.

The Front Cover illustrates ultrafast spectroscopic insights into the photoexcited energy relaxation pathways of St. John's wort-derived fluorescent photosensitizer hypericin in solution. The bidirectional excited-state intramolecular proton transfer (ESIPT) gains prominence after UV excitation with enhanced photoprotection in a “proton pachinko”, whereas visible excitation results in more phototoxicity. More information can be found in the Research Article by C. Fang and co-workers (DOI: 10.1002/chem.202500639). Cover design by S. Johnson and C. Fang.

In silico studies support the experimental findings of our acetone-sensitized electrocyclization reactions of perfluoroalkyl-substituted triphenylamines (TPAs) into perfluoroalkyl-substituted carbazoles. The calculations predicted that the substituents affect the regioselectivity and the reactivity of TPAs during the photoinduced [6π]-electrocyclization reaction due to changes in the electron density distributions. More information can be found in the Research Article by S. M. Bonesi, A. Postigo and co-workers (DOI: 10.1002/chem.202500133).

The Front Cover showcases a synthesized ultra-microporous organic-linked zincophosphate material that maintains high stability under extreme conditions and is effectively applied in carbon dioxide separation. The image abstractly represents the material′s microporous structure, emphasizing its potential in gas separation. More information can be found in the Research Article by P. Berilyn So, T.-H. Chen, H.-T. Chen, D.-Y. Kang, C.-H. Lin and co-workers (DOI: 10.1002/chem.202500136).

The Cover Feature highlights the activation of n–π* transitions in graphitic carbon nitride (g-C₃N₄). A schematic diagram illustrates the n–π* electronic transition pathways. By facilitating n–π* transitions, the absorption edge of g-C₃N₄ is successfully extended, enhancing its photocatalytic activity. More information can be found in the Review by Y. Sun, Z. Li, Y. Yuan and co-workers (DOI: 10.1002/chem.202500297).

“Uh? Just a box!” Stealth polymer nanofibers show great promise for therapeutic delivery; however, they remain hard to functionalise. In their Research Article (DOI: 10.1002/chem.202500108), S. T. G. Street, S. M. Willerth and co-workers explain how they harnessed light-catalysed PET-RAFT polymerization and crystallization-driven self-assembly to synthesize precision stealth nanofibers that are easy to modify, exhibit little toxicity, and display minimal interaction with U-87 MG cells.

The molecular structures of the complexes [CrMn(CO)₁₀]⁻ and [MnFe(CO)₁₀]⁺ complete the series of dimetal decacarbonyls reaching from [Cr₂(CO)₁₀]²⁻ to [Fe₂(CO)₁₀]²⁺. In our interpretation of the Wanderer above the Sea of Fog, a chemist is hiking through the dimetal-decacarbonyl landscape, discovering the hidden heterodinuclear complexes in the fog. The fog also highlights the misty borderline situation between covalent and Lewis-pair bonding, onto which light is ornately shed. In the background, the vibrational mountain range of the title compound shows its peaks. More information can be found in the Research Article by I. Krossing and co-workers (DOI: 10.1002/chem.202500489).

UHRF1 is a promising epigenetic target in oncology, but inhibitor development has proven challenging due to the interplay between its tandem Tudor domain (TTD) and plant homeodomain (PHD). The TTD binds trimethyllysine (Kme3) at position 9 while the PHD binds Arg at position 2 on histone 3. Herein, we report how the PHD influences TTD recognition of the histone 3 tail containing Kme3 (H3K9me3) versus its neutral isostere, tert-butyl norleucine (tBuNle). Our findings show that the dual domain binds both peptides equally, supporting tBuNle's potential for inhibitor development. However, unexpectedly, the binding mechanism of H3K9me3 differs between the single and dual domains. In the TTD alone, Kme3 is bound in the aromatic cage via electrostatically tunable cation-π interactions, but in the dual domain, Kme3 binding is independent of electrostatics in the aromatic cage-an unprecedented observation. Computational studies suggest cation-π interactions should contribute in both cases. The contrasting experimental and computational results point to an unusual example of negative chelate cooperativity: interactions between the histone and PHD mask the mechanism of TTD recognition of K9me3. This work underscores the complexity of histone PTM readout in multi-domain proteins and demonstrates the first example of a masked cation-π interaction.

Photocatalytic CO2 reduction offers a promising strategy to mitigate the greenhouse effect, yet it remains a challenging process due to the high energy barrier associated with the high stability of CO2. In this study, we synthesized Py-bTDC, a pyrene-based covalent organic framework (COF) enriched with nitrogen and sulfur atoms, and anchored palladium nanoclusters (Pd NCs) onto its structure to enhance CO2 reduction efficiency. The confined Pd NCs amplify the built-in electric field (IEF), enabling efficient photogenerated carrier migration and suppressing electron-hole recombination. Simultaneously, Pd NCs serve as catalytic active sites, optimizing CO2 adsorption and activation. Density functional theory (DFT) calculations reveal that Pd reduces the energy barrier for forming the critical intermediate (*COOH), thereby accelerating CO production. Under visible-light irradiation in a gas-solid system using water as a proton donor, the Pd3/Py-bTDC composite achieved a CO evolution rate of 17.75 μmol·h-1·g-1 with 86.0% selectivity. This study advances the design of COF-based photocatalysts by synergistically modulating IEF and the engineering active sites for efficient CO2 reduction.

The hand you are dealt: Reduced Tc^V/Re^VI octahedra and fully oxidized Tc^VII/Re^VII tetrahedra self-assemble, mix and match, and exchange to produce the first group VII technetium/rhenium mixed metal polyoxometalate and the first rigorous characterization of a rhenium autoreduction product. Based on both the lability of the polynuclear clusters and trends in reduction, the expansion of nascent group VII polyoxometalates is promising. More information can be found in the Research Article by M. Nyman and co-workers (DOI: 10.1002/chem.202404144).