European Journal of Inorganic Chemistry最新文献

Ammonia was first discovered as a chemical solvent in the 19th century. Extensive investigations during the 20th century toward its physical and chemical properties have yielded substantial knowledge regarding the compound. Historically, its merit was mainly seen in chemical synthesis and its ability to accommodate syntheses that could not be pursued in aqueous solvents. With a growing demand for low-emission energy systems, the scientific focus on ammonia shifted toward its potential for efficient hydrogen storage and transportation, as well as for direct combustion. Herein, a brief overview of the development of the role of ammonia, with the goal of highlighting its unique properties as a solvent, is provided, in particular, in the chemical syntheses of unprecedented species and reactive compounds.

Nonlinear optical (NLO) crystals play a pivotal role in solid-state lasers and have broad applications in both civilian and military technologies. Ideal NLO crystal materials should possess a wide transmission range, moderate birefringence, a high second-harmonic generation (SHG) coefficient, and excellent physical and chemical stability. Recent research has highlighted that incorporating metals with stereochemically active lone pairs (SCALPs) can significantly improve the NLO performance of these materials. This review presents a comprehensive overview of the latest 20 years’ advancements in NLO crystals featuring SCALPs, with a focus on their crystal structures and optical properties, particularly their SHG responses. The article also explores how metal-based functional units containing SCALPs influence the polarizability of these materials. It is anticipated that this review will provide valuable insights into the functional design of high-performance NLO crystals, contributing to the discovery of new SHG materials with the desired properties to meet the growing demands of modern technologies.

Room-temperature facile synthesis of CsNiCl₃ is successfully achieved to tune its magnetic, optical, and electrochemical properties by the incorporation of Fe²⁺-ion in the lattice. To ensure phase purity, the synthesized CsNiCl₃ is characterized using powder X-ray diffraction, followed by Rietveld refinement, Fourier transform infrared, Raman spectroscopy, and UV-vis diffuse reflectance measurements. To assess the uniformity of the Fe doping and its oxidation state, field emission scanning electron microscopy mapping and X-ray photoelectron spectroscopy are performed, confirming that Fe²⁺-ions are homogeneously distributed within the lattice. The field and temperature dependent magnetic studies on the doped CsNiCl₃ reveal the presence of spin glass behavior at 52.7 K; the effect can be explained based on intermolecular interaction between nickel and ferrous ions and consequently reduction in spin frustration is observed, in contrast to the magnetic phase transitions observed in the undoped compound at 45.7 and 31.9 K. Moreover, photoluminescence studies indicate the emergence of red emission in CsNi_1−xFe_xCl₃ (x = 0.05, 0.10, and 0.15) with an increase in luminescence lifetime correlating with higher dopant concentration. Electrochemical analysis further reveals that the doped sample enhances ionic conductivity while decreasing diffusional resistance, suggesting potential applications in battery and sensor technologies.

Detailed ab initio CASSCF calculations coupled with periodic density functional theory studies on [(Cp*)Dy(Cp^iPr5)]⁺ molecule encapsulated in a metal-organic framework (MOF) revealed that MOF encapsulation offers stability to these fragile molecules, keeping intact the U_eff (barrier height for magnetization reversal) values. Most importantly, this encapsulation suppresses the key vibrations responsible for reducing the blocking temperature, offering a hitherto unknown strategy for a new generation of SIM-based devices.

A novel hybrid pentaphosphomolybdate copper complex C_7.5H_36.3Cu_1.3Mo₅N₃O_31.4P₂, abbreviated as (H₂MP)_1.5[Cu_1.3P₂Mo₅], featuring a honeycomb Kagome (HK) lattice, is synthesized in aqueous solution. Single-crystal X-ray diffraction analysis reveals structural defects associated with the nonstoichiometric occupancy of copper ions and water molecules. The compound crystallizes in the monoclinic space group P2₁/c, with the asymmetric unit comprising two distinct Cu(II) ions (one occupying the Wyckoff position 4e and the other 2d, with an occupancy ratio of ≈60%), along with one and a half 2-methylpiperazinium cations, a unique Strandberg-type [P₂Mo₅O₂₃]⁵⁻ anion, 4.2 coordinated water molecules, and 3.48 lattice water molecules. The negative Curie–Weiss temperature, derived from the high temperature magnetic susceptibility data, indicates the presence of antiferromagnetic interaction between Cu²⁺ moments. Additionally, the observed power law behavior and magnetization data collapse are indicative of a random singlet state, suggesting the presence of a quantum spin liquid ground state. Electronic structure calculations show that the conduction band is primarily derived from Mo(4d) states while the valence band arises from a strong hybridization between N(2p), Cu(3d), and O(2p) orbitals. The experimental bandgap, estimated using Kubelka–Munk theory, reveals three prominent optical transitions in the ultraviolet-visible region at 2.6, 2.96, and 3.24 eV.

This review aims to highlight over three decades of research on the use of phosphonate and arsonate ligands in designing uranyl nanotubules and nanospheres. It discusses the synthesis, structures, properties, as well as how earlier compounds provide valuable insights into the formation of subsequent ones. In general, phosphonate and arsonate derivatives exhibit flexibility, which enhances the curvature of the structural units within uranyl polyhedra. Notably, earlier uranyl phosphonate nanotubules feature a nearly circular cross-section, whereas some recent examples display highly elliptical shapes. The emergence of structurally dynamic polymorphs capable of reversible phase transformations reflects a growing sophistication in synthetic design. Ion-exchange studies further underscore the robustness and reusability of these materials, marking a shift from esthetic curiosity to functional utility. A synergistic interplay between peroxo and phosphonate ligands is key to the stabilization of unique uranyl topologies. While some uranyl cage assemblies arise serendipitously through the use of bulky ligands, a more intentional design approach is achieved through in situ ligand condensation reactions.

The present work highlights the development of one Cu(II) complex [CuL(μ1,3-N3)]_∞ (complex 1) and Cu(I) complex [Cu₂L₂(H₂O)₂Ph(COO)₂] (complex 2) by using Schiff base HL, synthesized by the simple condensation reaction of 2-aminoethyl piperazine and 5-bromo salicylaldehyde, in the presence of sodium azide and terephthalic acid, respectively. The single-crystal data analysis reveals that complex 1 comprises an end-to-end azido-bridged polymeric network, whereas in complex 2, one ligand, one water molecule, and one deprotonated acid moiety coordinate to the Cu(I) center, resulting in a distorted trigonal bipyramidal geometry. Herein, two Cu(I) centers are connected by deprotonated terephthalic acid, forming a dinuclear complex. After rigorous characterization, the DNA and protein binding potentiality of both complexes is confirmed by using several biophysical studies, including ultra violate (UV), fluorescence, and circular dichroism titration, and a DNA melting study. Higher complexes–macromolecules binding constant values of complex 2 approve its higher association ability to both macromolecules. Molecular modeling studies corroborate the experimental findings. Furthermore, the 3-(4,5-dimethylthiazolyl-2)-2,5-diphenyltetrazolium bromide (MTT) assay study gives a solid stamp of the significant anticancer property of complex 1 toward two cancer cell lines, which is confirmed via an MTT assay study. Good reactive oxygen species generation ability is most probably the main reason for showing a good anticancer property of complex 1.

The Front Cover reinterprets the famous Town Musicians of Bremen as alchemists, synthesising and crystallising various chlorides of ferrocene-pnictogen compounds. The donkey and the dog are inspecting the crystals, while the cat fell asleep after thinking about the molecular structure of Fc₂SbCl₄. In the background, the rooster is checking the reaction equations. More information can be found in the Research Article by J. Beckmann and co-workers (DOI: 10.1002/ejic.202500216). Artwork: a dry pastel drawing by Żaneta Wawrzyńczak.

Chiral lanthanide(III) complexes with superior circularly polarized luminescence (CPL) properties, especially for the efficient chiral europium(III) complexes with high dissymmetry factor (g_lum) obtained by rational design of coordination ligands, are important in the field of chiral functional materials. In this work, the β-diketone ligand 1,1,1-trifluoro-3-(2-thenoyl)acetonato (TTA) is used as the primary ligand and three axially chiral enantiomeric pairs, R/S-[1,1′-binaphthalene]-2,2′-diylbis(diphenylphosphine oxide) (R/S-BINAPO), R/S-(6,6′-dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine oxide) (R/S-BINAPO), and R/S-[4,4′-bibenzo[d][1,3]dioxole]-5,5′-diylbis(diphenylphosphine oxide) (R/S-DiO-BIPHPO), are used as ancillary ligands for three pairs of chiral Eu(III) enantiomers. The photoluminescence efficiencies of Eu(TTA)₃(BINAPO), Eu(TTA)₃(MeO-BIPHPO), and Eu(TTA)₃(DiO-BIPHPO) are as high as 0.49, 0.42, and 0.56, respectively. Furthermore, Eu(TTA)₃(R/S-BINAPO), Eu(TTA)₃(R/S-MeO-BIPHPO), and Eu(TTA)₃(R/S-DiO-BIPHPO) enantiomers exhibit symmetric CPL spectra with g_lum factors at the magnetic-dipole transition (⁵D₀ → ⁷F₁) as high as 0.067/–0.070, 0.128/–0.131, and 0.138/–0.147, respectively. These results suggest that an effective ligand-to-metal energy transfer occurs, and the chiral ancillary ligands affect the chiroptical properties of the Eu(III) enantiomers effectively.

Stimuli-responsive phase transition materials exhibiting reversible switching between distinct dielectric states have emerged as promising candidates for applications in memory storage, logic circuits, and smart sensors. However, a fundamental challenge remaining is the lack of in-depth understanding of the structure-property relationships that govern phase transitions. Herein, a comparative study of three pyridine-based copper (II) bromide compounds is given, [C₅NH₆]₂[CuBr₄] (1), [CuBr₂(C₅NH₅)₂] (2), and [(C₅NH₆)₂(18-crown-6)₂][CuBr₄] (3), falling into three different structural categories: a zero-dimensional organic–inorganic hybrid, a coordination complex, and a supramolecular host-guest compound, respectively. Among them, only compound 1 has a distinct order–disorder phase transition accompanied by switchable dielectric property. Structural analyses and Hirshfeld surface studies reveal that the loosely packed hybrid framework of compound 1 enables moderate intermolecular interactions and sufficient motional freedom of the pyridinium cations, thereby dominating the phase transition. In contrast, for compounds 2 and 3, such molecular motions are significantly suppressed by the stronger coordination bonding or hydrogen bonds. These findings emphasize the decisive role of competition between molecular motions and suitable intermolecular interactions in modulating structural phase transitions, offering valuable insights into the crystal engineering of functional materials with dielectric switching behaviors.