European Journal of Inorganic Chemistry最新文献

Developing cost-effective electrocatalysts for the oxygen evolution reaction (OER) is crucial for scalable water electrolysis. Herein, calcium oxide (CaO) and phosphate frameworks are engineered with iron sourced from rust to fabricate two catalysts: CaOFe and CPFe (KCaPO₄-Fe) derived from marine biowaste. While CaOFe features surface-dispersed Fe species, CPFe integrates Fe into the phosphate matrix (KCaPO₄). Comprehensive structural, morphological, and surface analyses confirm distinct environments for Fe incorporation. Extensive electrochemical studies reveal a unique performance crossover: CPFe exhibits superior activity at low overpotential (η₁₀ = 297 mV) with a Tafel slope of (147 mV dec⁻¹), whereas CaOFe outperforms at higher current densities (η₁₀₀ = 424 mV) with a lower Tafel slope (107 mV dec⁻¹), attributed to enhanced kinetics via surface Fe. Impedance and Bode plot analyses further confirm distinct charge-transfer dynamics between the two catalysts. Overall, this work demonstrates how the local environment of iron governs electrocatalytic behavior, by providing mechanistic insights into tuning OER performance through waste-derived bimetallic systems.

The Front Cover presents polymorphic zinc-bound amyloid-β (Aβ) dimer models, derived from an extensive computational study of the molecular basis of zinc-induced Aβ primary nucleation. By revealing how zinc ions influence Aβ dimer structure and stability, the Research Article by K. Abramov Harpaz and Y. Miller (DOI: 10.1002/ejic.202500331) provides new insights into the mechanisms driving early aggregation events in Alzheimer’s disease, offering a molecular framework for future therapeutic strategies.

Chronic hyperglycemia resulting from impaired blood glucose homeostasis is a hallmark of diabetes mellitus (DM). In particular, type II DM is characterized by insulin resistance, in which cells fail to appropriately respond to normal or even elevated levels of insulin. Despite advances in pharmacological interventions, current approaches to treating DM provide only temporary symptomatic relief and cannot completely cure the disease, highlighting the need to reveal fundamental pathological mechanisms governing the endocrine system. Glucose homeostasis is regulated by the combined actions of pancreatic islet-derived peptide hormones (e.g., insulin, islet amyloid polypeptide, somatostatin, glucagon, pancreatic polypeptide, and ghrelin), and disruption of their interplay has been implicated in the molecular pathology of DM. Moreover, the bioavailability and distribution of transition metal ions can be altered in diabetic conditions, suggesting the potential interactions between metal ions and pancreatic hormones. In this review, we cover the coordination chemistry of these peptide-based hormones and summarize how their metal-binding properties influence conformational dynamics, misfolding, aggregation, and downstream cellular signaling pathways.

In spite of wide-ranging applications in various fields, the high reactivity and difficulty in storage of elemental fluorine pose significant safety concerns, creating a strong demand for safe, small-scale, and on-site generation methods. Herein, the electrochemical behavior of SnF₂ dissolved in CsF-2.45HF molten salt is investigated as a fluoride source for F₂ gas production by electrolysis of a metal fluoride in view of the use of low valence metal fluorides. SnF₂ exhibits a solubility of 0.31 mol kg⁻¹, slightly higher than that of CuF₂ previously utilized for this purpose. Cyclic voltammetry and potentiostatic electrolysis show that Sn(II) is reduced to metallic tin without H₂ gas evolution in this medium, indicating its suitability for cathodic metal deposition. On the other hand, F₂ gas production is suppressed on the anodic side, as the generated F₂ readily reacts with Sn(II) to form Cs₂[Sn(IV)F₆]. A system in which the anodic and cathodic compartments are separated by a solid fluoride-ion conductor is proposed to address the issue of Sn oxidation. This study contributes to the advancement of compact and secure electrochemical systems for the practical handling of F₂ gas under mild conditions.

A series of pyridine-based unsymmetrical 1,3 disubstituted benzimidazolium bromides have been synthesized as N-heterocyclic carbene (NHC) precursors. These compounds have been used for the synthesis of three novel pyridyl–NHC complexes—Ru–Py–CH₃, Ru–Py–CF₃, and Ru–Py–H—which have been characterized. The complexes have been observed to be air-stable and show catalytic activity toward the N-alkylation of amines using alcohols under air. Notably, Ru–Py–CH₃ has been found to be very efficient toward the N-alkylation of various amines at 0.75 mol% loading, activated by 20 mol% NaO^tBu. A large variety of amines are converted to secondary amines with good yield on coupling aromatic and aliphatic alcohols. Detailed control experiments and mechanistic pathway studies are provided to offer more insights into the reaction mechanism, which has been found to follow a green hydrogen autotransfer pathway.

Aluminum–element multiple bonds represent a rapidly expanding frontier in main-group chemistry, expanding the scope of aluminum from its conventional role as a highly electropositive, single-bonded element. Through the development of sterically demanding and electronically tailored ligands, a variety of species bearing Al–B, Al–Al, Al–C, Al–N, and heavier Al–E (E = Si, P, As, and chalcogens) bonds have been successfully isolated and characterized. These compounds display diverse bonding patterns, ranging from highly polarized covalent linkages to delocalized multicenter frameworks, as elucidated by crystallographic, spectroscopic, and computational analyses. Their reactivity often departs from classical aluminum chemistry, characterized by ambiphilic behavior that enables transformations including small-molecule activation and novel bond-forming reactions. This review summarizes recent synthetic strategies, structural and bonding analyses, and the distinctive reactivity patterns of aluminum–element multiple bonds, and discusses the correlations between electronic structure and chemical behaviors. Continued advances in this area are expected to broaden the accessible chemical space and open pathways to functional molecular systems with potential applications in catalysis, materials development, and beyond.

Herein, the simple synthesis of triel dihydride complexes with the sterically demanding 1,5,9-trimesityldipyrromethene (^MesDPM) ligand is reported. With these compounds, reactivity studies are carried out, opening access to new classes of ^MesDPM triels. All compounds are fully characterized by standard analytic methods such as NMR, IR, and UV/vis spectroscopy as well as mass spectrometry. In addition, the molecular structures in solid state are determined by single-crystal X-ray diffraction analysis. In some instances, green fluorescence can also be observed upon solar irradiation, which prompted further investigations of the photoluminescence behavior.

The Front Cover depicts the formation process of a three-dimensional coordination polymer derived from crown ether-appended tetraazanaphthacenes. The crown ether moieties first capture metal ions; this is followed by electrochemical reduction of the framework. Finally, the resulting radical anion ligands self-assemble into a three-dimensional coordination polymer structure. More information can be found in the Research Article by K. Isoda, T. Sugaya, M. Tadokoro and co-workers (DOI: 10.1002/ejic.202500332). Illustration by K.I.

The synthesis of sterically demanding 2,6-bis(2,4,6-trimethylphenyl)phenyl (Ter)-stabilized potassium phosphinophosphido dithioformates 1a–b K[TerP(CS₂)PR₂] via conversion of the corresponding potassium phosphinophosphides K[TerP–PR₂] (R = iPr, tBu) with CS₂ is reported. In solution, the dithioformates 1a–b undergo a migration reaction, resulting in the formation of anionic phosphanylthioketones, K[TerPC(=S)–P(S)R₂] (2a-b), bearing phosphanylthiolate groups. The cocrystallization of compounds 1a and 2a allows simultaneous structural characterization of both, and the crystallization of 2a from THF or benzene affords specific solvates with solvent-dependent discrete dimers or polymeric chains, respectively.

Halogen-directed crystallization of Cu(I) coordination polymers (CCP-X, X = Cl, Br) enables efficient visible-light-driven photocatalytic amine-to-imine, in which CCP-Br exhibits superior photocatalytic performance to CCP-Cl due to enhanced charge separation and superoxide radical (O₂^•−) generation, demonstrating a halogen-modulation strategy for photocatalytic polymer design.