European Journal of Inorganic Chemistry最新文献

All solid-state batteries are becoming increasingly prevalent in recent energy storage research due to their enhanced safety, higher energy density, wider operating temperature ranges, in addition to a longer cycle life compared to standard Li-ion batteries. Nevertheless, numerous properties require enhancement for this novel technology to reach its full potential, especially the solid electrolyte (SE) field. For example, further research is required in the following areas: ionic conductivity, mechanical properties, and interface stability with the electrolyte and the lithium metal (Li) anode. One proposed approach to enhancing SE properties is fluorination. The incorporation of fluorine can result in enhanced electrochemical stability, attributed to the formation of a lithium fluoride (LiF) interface between the electrolyte and the Li anode. Additionally, fluorine doping can increase ionic conductivity due to its high electronegativity, facilitating the mobility of lithium ions. This review examines the impact of fluorine incorporation on SE properties, focusing on ionic conductivity and electrochemical stability. Furthermore, the limitations of fluorination in electrolytes, particularly with the LiF formation, will be discussed.

A series of layered perovskites K_2−xH_xEu₂Ti₃O₁₀ (0 ≤ x ≤ 2) belonging to the Ruddlesden–Popper family of phases was synthesized using solid-state and ion exchange methods. The phase and chemical purity of the compounds were proved by X-ray diffraction and energy-dispersive X-ray microanalysis. The hydrolytic stability of the K₂Eu₂Ti₃O₁₀ compound was studied upon contact with air and aqueous solutions. The structural changes were determined using differential thermal analysis and IR. The protonated form H₂Eu₂Ti₃O₁₀ was obtained by leaching the potassium-containing phase in a heated hydrochloric acid solution. The crystal structure of K₂Eu₂Ti₃O₁₀ was refined using the Rietveld method. Structural distortions have been quantitatively described. The optical bandgap, valence band edge, and conduction band edge potentials of the obtained compounds were calculated from diffuse reflectance spectroscopy data. A photocatalytic experiment of methylene blue degradation under ultraviolet light was conducted.

Reaction of the bis(gallylene) 1 with azobenzene and the triphosphirane (PMes)₃ gives rise to the bis(spirocycle) 2 and the 1,2-diphospha-3,4-digalletane 4, respectively. These findings highlight the ambident reactivity of the bis(gallylene) as its two low-valent gallium centers react individually in the first case, while the cooperation of both metal centers is necessary in the second case. Both reaction products have been fully characterized, including single-crystal X-ray diffraction analysis as well as NMR and IR spectroscopy. Remarkably, when 2 is dissolved in acetonitrile, tautomerism along with rearomatization is observed, thereby affording 3 as evidenced by single-crystal X-ray diffraction analysis.

Two manganese cyanurate compounds, Mn(H₂C₃N₃O₃)₂(H₂O)₄ and Mn(H₂C₃N₃O₃)₂(H₂O)₇ were prepared and structurally characterized. The thermal conversion cascade of Mn(H₂C₃N₃O₃)₂(H₂O)₄ is explored by combined differential thermoanalytic and thermogravimetric studies, revealing this compound as a useful precursor for the formation of pure Mn(CN₂). During this process, manganese monohydrocyanurate Mn(HC₃N₃O₃) (MHCY) appears as a new compound that was refined to crystallize in a noncentrosymmetric space group. The noncentrosymmetric space group and the presence of a cyanurate ring gave rise to the study of the second-order nonlinear susceptibility of MHCY single crystals, revealing a remarkable second harmonic generation response.

In this work, we report the synthesis of new cobalt tetraphenylporphyrinate-chitosan-based microspheres for application as biosensors and in anticancer therapy. These microspheres were characterized using optical microscopy, scanning and transmission electron microscopy, and X-ray powder diffraction. We analyzed their nonlinear optical behavior, specifically the second harmonic generation (SHG), employing a high-resolution SHG microscope, with the quadratic fits of the SHG intensities considered as a function of the excitation power, under optimized experimental conditions. Beyond the typical porphyrinate fluorescence, the microspheres exhibit the same peculiar SHG behavior as CoTPP powder, making them suitable as multibiosensors. Additionally, they exhibit the same laser-induced dynamic properties previously observed in CoTPP powder, indicating their promising potential for dynamic anticancer therapies. The results of this work are encouraging, highlighting the possible application of these microspheres as multibiosensors and anticancer agents.

Well-defined alkyne complexes of transition metals that can be accessed across multiple oxidation states remain rare. This scarcity motivates the targeting of new systems for systematic characterization and reactivity studies. In this report, we describe the synthesis and characterization of both monometallic and bimetallic ruthenium complexes supported by a bisphosphine alkyne pincer ligand. Electrochemical study of a subset of the synthesized compounds revealed accessible redox events, suggesting that odd electron count alkyne adducts may be chemically feasible for these systems. Efforts to synthesize paramagnetic ruthenium alkyne adducts supported by the bisphosphine-alkyne ligands are also discussed.

A porphyrin nanotube (PNT) of composition Cd₂(TPyP)(sez)₂ (TPyP = 5,10,15,20-tetra(4-pyridyl)porphyrin, sez = 1,2,5-benzoselenadiazole-5-carboxylate) has recently been shown to be a robust crystalline adsorbent for a variety of guests. The assorted molecular and metal components of the tube may be substituted with other units which yield structurally similar materials. These new variations of the original nanotubes are obtained by incorporating different metal centres within the porphyrin macrocycles, as well as employing other organic bridging and penetrating ligands. All derivatives crystallise as structurally similar nanotubes. The study has been extended to examine the crystallographic impact of the inclusion of solvent molecules. This work further illustrates the remarkable persistence of this type of porous assembly despite the integration of a variety of molecular building blocks. The investigation provides a strong indication that this family of PNTs is potentially enormous, offering the opportunity to tailor the host properties for specific purposes.

Herein, the reactivities of different carboranylthioamide ligands with Rh/Ir half-sandwich precursors were explored. The results revealed that Rh activated the B(3)H bond in the o-carboranylthioamide ligand, forming a dinuclear metallacycle. However, when the N atom's site was changed in the pyridine group, deboronization occurred. Additionally, when more stable m- and p-carboranylthioamide ligands were used, a linkerless tetranuclear metallacycle possessing an activated B(2)H bond was formed, revealing the capability of the rigid carborane skeleton to precisely control the metallacycle topology and providing a universal paradigm for designing ligand space programing in supramolecular assembly.

Systematic studies of metal complexes of tau protein fragments may contribute to gaining more information about its role in the neurodegenerative tauopathies. Previous studies have confirmed that the tau fragment containing the amino acid His32 has a higher metal binding affinity than other fragments containing histidine, due to the presence of a threonine near the histidine. In order to investigate the role of threonine in more detail, the Cu(II), Zn(II), and Ni(II) complexes of the tau(371–376) fragment (Ac-IETHKL-NH₂) and three tau(29–34) mutants (Ac-ATAHQD-NH₂, Ac-ATMHQD-NH₂, Ac-AAMHQD-NH₂) were examined. The presences of -TXH- moiety resulted in a small increase in the stability of the imidazole coordinated complexes as well as an observable change in the CD and UV–Vis spectra for copper(II) and nickel(II) complexes. On the other hand, the binding of nickel(II) ion to the –TXH– part of the molecule may induce hydrolytic processes in peptides. The hydrolytic process was studied in the presence of nickel(II) under different condition in peptides containing –TXH– and –XTH– moiety. The Ni(II)-induced hydrolytic process was obvious in the case of peptide containing –TXH– sequence in alkaline medium. However, the tau(371–376) fragment containing –XTH– sequence did not show any hydrolytic activity in the presence of Ni(II).

Three clamshell binuclear Pd(II) complexes have been synthesized using the primary cyclometallating ligands of phenylpyridine (ppy) and its derivatives with the ancillary clamping ligand of 3,5-di-tert-butyl-1H-pyrazole (dbp). All three complexes are fully characterized by nuclear magnetic resonance, high-resolution mass spectrometry, cyclic voltammetry, and single-crystal X-ray diffraction, and the crystal structures exhibited the Pd–Pd distances between 2.813 to 2.882 Å. It is a pioneering report of a group of binuclear Pd(II) complexes showing intensive triplet emission between 635 to 764 nm with the nature of metal-metal-to-ligand charge transfer at room temperature.