Russian Journal of Inorganic Chemistry最新文献

The double complex salt [Rh(NH₃)₆][Fe(CN)₆] has been structurally characterized. The thermal behavior of salt [Rh(NH₃)₆][Fe(CN)₆] in reducing (He/H₂), inert (He), and oxidizing (Ar/O₂) atmospheres has been studied in detail. The intermediate product of the decomposition of double complex salts [M(NH₃)₆][Fe(CN)₆] (M = Ir, Rh) has been found to be an X-ray amorphous polymer compound with the gross composition FeM(CN)₅. The final product of the decomposition of [Rh(NH₃)₆][Fe(CN)₆] in reducing and inert atmospheres is an ordered FeRh alloy. In an oxidizing atmosphere, a solid solution of Fe₂O₃ and Rh₂O₃ oxides is predominantly formed. The obtained data allow us to consider double complex salts as precursors for obtaining iron-iridium and iron-rhodium alloys or oxide systems based on them.

Two coordination polymers (CPs) {[Zn₂(HL)(btc)(H₂O)₂].4(H₂O)}_n (1) and {[Zn(H₂L)(btec)_0.5](H₂O)}_n (2) have been synthesized under hydrothermal conditions by using 3-(1H-pyrazol-4-yl)-5-(pyridin-4-yl)-1,2,4-triazole (H₂L), 1,3,5-benzenetricarboxylic acid (H₃btc) and 1,2,4,5-benzenetetracarboxylic acid (H₄btec) as reagents along with zinc acetate. Compounds 1 and 2 have been characterized by elemental analysis, single crystal X-ray diffraction, and IR spectroscopy. Compound 1 shows a corrugated layered structure, and a 3D supramolecular architecture is further assembled in 1 via hydrogen-bonding contacts. Compound 2 exhibits a 3D framework structure. The thermal behavior and the luminescence properties of the two compounds were studied.

In this study, synthesis and characterization of electrolytes containing lithium oxide incorporated by Ge³⁺ with a basic formula of Li_0.8Ge_0.2–xO_1.9 (where x is equal to 0.05, 0.10, 0.15) and doped lithium with Ca²⁺ and Mg²⁺ ions using Li_1−xM_xO_2−δ (M = Ca, Mg) formula were produced through simple and cost-effective co-precipitation method. All the samples exhibited a perfect match with the rhombohedral-type structure, also demonstrating a good crystalline nature were examined using X-ray powder diffraction. The radii of the Li³⁺ (0.76 Å) and Ge³⁺ (0.53 Å) ions are almost close to that of Ca²⁺ and Mg²⁺. Further, structural modifications were investigated through Raman spectroscopy. The measurements recorded within the spectral range of 50 to 1000 cm^–1, offer a comprehensive view of the vibrational characteristics of these materials. Minor functional group modifications were identified by FT-IR analysis. Optical absorption spectra were obtained from LiO₂ electrolyte samples doped with varying concentrations of Ge³⁺, Ca²⁺ and Mg²⁺ ions, covering a wavelength range of 200 to 800 nm. The study utilizes SEM and EDAX to provide an in-depth investigation of the morphology and elemental composition of LiO electrolyte samples co-doped with varying concentrations of Ge³⁺, Ca²⁺ and Mg²⁺ ions. The EDAX spectrum confirms the presence of Li, Ge, Ca, and Mg elements, validating the doping process and ensuring the accuracy of the sample preparation. The role of individual grains and grain boundaries in the overall conductivity was explored through AC impedance spectroscopy, conducted over low temperature range.

Halide perovskites have drawn considerable attention for their exceptional properties and the flexibility to fine-tune their composition. In this study, we use first-principles density functional theory (DFT) calculations with the WIEN2K code to investigate the structural, electronic, optical, and mechanical properties of cubic halide perovskites AlGeX₃ (X = Cl, Br), exploring their potential for optoelectronic applications. Replacing Cl with Br alters the lattice parameters and unit cell volume, highlighting the role of halogen chemistry in shaping structural behavior. Electronic structure analysis confirms a direct bandgap, with values of 2.13 eV for AlGeCl₃ and 1.96 eV for AlGeBr₃, making them suitable for ultraviolet optoelectronics. Optical results reveal strong absorption, excellent electrical conductivity, and low reflectivity, making these materials promising for light-harvesting applications. Mechanical assessments, including bulk modulus (B), shear modulus (G), Young’s modulus (E), anisotropic factor (A), Poisson’s ratio, and Pugh’s ratio (B/G), confirm that these materials maintain a stable balance between stiffness and ductility. Additionally, the Debye temperature (θ_D) suggests strong thermal resilience, while formation energy calculations reinforce their thermodynamic stability. Overall, AlGeX₃ (X = Cl, Br) emerges as a strong candidate for next-generation photodetectors and high-performance optoelectronic devices.

A new vanadium (V) complex [VO(dipic)(hpo)(H₂O)] (1) (where “dipic” is dipicolinate and hpo is 1-(2-hydroxyphenyl)ethanone oxime) is synthesized with a oxime moiety and dipicolinato anion as ligands. Using single crystal X-ray diffraction technique, the structure of the complex 1 is determined. The theoretically optimized structure of the complex is obtained from DFT calculations predicting a distorted pentagonal-bipyramidal geometry. Theoretically predicted structure is in excellent match with the experimentally obtained structure utilizing X-ray single crystal diffraction analysis. Frontier molecular orbital (FMO) analysis, molecular electrostatic potential (MEP) are performed to understand the stability and reactivity characteristics of the complex. The simulated UV-Vis maximum absorption wavelength from TDDFT method is in excellent agreement with the experimentally observed λ_max. Hirshfeld surface analysis indicates hydrogen bonding involving O–H( cdots )O interactions play major role in stabilizing the molecular crystal. Interesting non-covalent interactions are revealed by a thorough examination of the complex’s solid state architecture. In the solid state, strong self-assembled complex formation is dependent on hydrogen bonding interactions, V⋯O, and V⋯N interactions.

A comparative analysis of ion transport mechanisms in crystals was carried out for three phases formed in the CaF₂–HoF₃ condensed system: a fluorite phase (the F-phase, CaF₂ and Ca_1–xHo_xF_2+x solid solution), a tysonite phase (the T-phase, Ho_1–yCa_yF_3–y solid solution), and a phase having the orthorhombic β-YF₃ structure (the R-phase, HoF₃). The ionic conductivity σ_dc(T) fundamental data gained in experiments on single-crystal samples was used to derive ionic conductivity versus composition and activation enthalpy of ion transfer versus composition dependences. A comparison of the properties of the components of the system under study shows that the conductivity of the HoF₃ R-phase (σ_{500 K} = 5 × 10⁻⁶ S/cm at 500 K) is five orders of magnitude that of the stoichiometric CaF₂ F-phase. In the region of the Ca_1–xHo_xF_{2 + x} (0 < x ≤ 0.35) nonstoichiometric F-phase, the interstitial mechanism of electrical conductivity occurs. The σ_{500 K} increases as the HoF₃ concentration increases to reach 4 × 10⁻⁵ S/cm at x = 0.35. The Ho_1–yCa_yF_3–y (y = 1 − x, x = 0.77) nonstoichiometric T-phase has σ_{500 K} = 2 × 10⁻⁴ S/cm, which is five and 40 times as high as the electrical conductivity of the Ca_0.65Ho_0.35F_2.35 F-phase and HoF₃ R-phase, respectively. The reasons for the rapid anionic transport in the nonstoichiometric T-phase are the ion vacancy electrical conductivity and extensive heterovalent isomorphism of cations.

A series of samples in the Y₂O₃–SnO₂ system with various yttrium and tin oxide ratios were synthesized using the solid-state method. The phase composition of the obtained samples was monitored by X-ray powder diffraction. The diffraction patterns were processed, and crystallographic parameters were calculated using the full-profile analysis method. The study of phase equilibria in the Y₂O₃–SnO₂ system at 1400°C allowed first the determination of the homogeneity range of yttrium stannate Y₂Sn₂O₇, which is shifted toward yttrium oxide and ranges from 33.3 to 36 mol % Y₂O₃. The existence of a solid solution based on cubic yttrium oxide extending up to 3 mol % SnO₂ was established. A comparative analysis of the influence of the substituting tetravalent cation radius on the homogeneity range of the solid solution based on yttrium oxide was conducted. The absence of yttrium oxide solubility in tin dioxide was noted.

Magnetic copper(II) ferrite nanoparticles are promising materials for biomedical, electronic, and photocatalytic applications. In this work, homogeneous spherical CuFe₂O₄ nanoparticles 18.3 ± 0.4 nm in size with a band gap of 2.37 eV have been synthesized by anion-exchange precipitation using an AV-17-8 anion-exchange resin in the OH form in the presence of dextran-40. The photocatalytic activity of the resulting material has been studied for photodegradation of a widely used anionic dye—indigo carmine—in the presence of sacrificial reagents: sodium citrate, carbonate, and hydrogen carbonate. Combined use of electron donors, sodium hydrogen carbonate and citrate, which reduce the probability of recombination of photogenerated holes and electrons, has turned out to be effective. The kinetic parameters of the process have been determined (pseudo-zero order, k_app. = 3.6 × 10^–7 mol/(L min), T_1/2 = 75.8 ± 2.3 min) and its mechanism has been elucidated. The intermediates of the photocatalytic oxidation of indigo carmine have been identified by NMR.

The co-reduction of platinum and nickel complex compounds with hydrazine hydrate in alkaline aqueous ammonia solutions was studied under hydrothermal autoclave conditions. It was established that quantitative precipitation of nickel and platinum occurred within 1 h at a temperature of 110°C. All phases formed upon the reduction had fcc lattices and ferromagnetic behavior. The formation of nickel−platinum substitutional solid solutions was proved by powder X-ray diffraction. The nickel to platinum molar ratio was varied from 16 : 1 to 0.5 : 1, and in all cases, two phases of the nickel−platinum substitutional solid solution were detected, namely, a phase of variable composition depending on the initial molar ratio of nickel and platinum with a lattice parameter of 3.622−3.772 Å, which corresponds to 25–62 at % platinum, and a platinum-enriched phase (90–95 at %) with almost invariable composition and a lattice parameter of 3.885–3.901 Å. For molar ratios from 16 : 1 to 1 : 1, in addition to two solid solution phases, a nickel metal phase with a crystal lattice parameter of 3.527 Å was clearly seen. When the initial ratio of nickel to platinum was 0.5 : 1, no nickel metal phase was found. Under hydrothermal conditions, nickel dissolved in 1 M hydrochloric acid, while solid solutions were chemically and structurally stable.

In the quasi-quaternary system BaO–Sc₂O₃–CuO–MoO₃, the possibility of obtaining phases with perovskite structure was investigated by varying the chemical composition, temperature, and annealing atmosphere. A perovskite-like solid solution Ba₄Sc₂CuMoO₁₁ with tetragonal structure was obtained by the gel combustion method followed by annealing in argon atmosphere at 900°C. Low-enthalpy solid-phase transformations of Ba₄Sc₂CuMoO₁₁ at 810–820 and 960–975°C were found by DTA-TG.