Žurnal neorganičeskoj himii

New mixed-ligand organometallic coordination polymers based on zinc terephthalate (bdc), 2-iodoterephthalate (bdc-I) and 1,4-diazabicyclo[2.2.2]octane (dabco) were obtained: [Zn₂(bdc)_1.67(bdc-I)_0.33dabco] (I), [Zn₂(bdc)_1.46(bdc-I)_0.54dabco] (II), [Zn₂(bdc)_1.12(bdc-I)_0.88dabco] (III), [Zn₂(bdc)_0.80(bdc-I)_1.2dabco] (IV), [Zn₂(bdc)_0.46(bdc-I)_1.54dabco] (V). Their structure and composition were determined by X-ray diffraction, X-ray phase, and elemental analysis. Compounds I–V are isostructural with [Zn₂(bdc)₂(dabco)], but not with [Zn₂(bdc-I)₂(dabco)], which we have not described previously, which is confirmed by X-ray phase analysis data. Experiments on the sorption of diiodine vapors are consistent with the idea that the presence of a larger amount of 2-iodoterephthalate in the MOF should lead to a decrease in pore volume: the greatest amount of I₂ is absorbed by I, and the smallest by V.

A new method for obtaining K₂Ce(PO₄)₂ ∙ xH₂O (s. g. I4₁/amd, a = b = 6.8300(2), c = 17.8488(4) Å, V = 832.63(4) ų, Z = 4) under hydrothermal conditions has been developed. It has been established that the thermolysis of this compound proceeds through three stages of mass loss with the formation of CePO₄ и K₄P₂O₇ as intermediate products, which upon further heating form a mixture of CePO₄ and K₃Ce(PO₄)₂. The calculated values of the sun protection factor and UVA protection factor for K₂Ce(PO₄)₂ ∙ xH₂O were 2.1 and 2.0, respectively. In relation to the human keratinocyte cell line (HaCaT), a photoprotective effect of K₂Ce(PO₄)₂ ∙ xH₂O was recorded. For the first time, the photoactive properties of KCe₂(PO₄)₃ and K₂Ce(PO₄)₂ ∙ хH₂O in the decomposition reaction of methylene blue were evaluated. A significant slowdown in the decomposition reaction of an organic dye was demonstrated when using K₂Ce(PO₄)₂ ∙ хH₂O.

The paper discusses the results of a study of the structural and thermophysical characteristics of polycrystalline ceramics produced from the InFeZnO₄ nanoparticles. It was found that the bulk density of the resulting material is ~86% of the theoretical one. Scanning electron microscopy has shown that it has a dense microcrystalline structure consisting of randomly oriented grains with dimensions of 5–20 µm. The thermal diffusivity of InFeZnO₄ ceramics was studied using the laser flash method. It was found that as the temperature increases from 299 to 1273 K, it decreases from 1.29 to 0.44 mm²/s. Using adiabatic and differential scanning calorimetry, the temperature dependence of the heat capacity of InFeZnO₄ was studied for the first time. It was established that the measured curve has no signs of the existence of phase transitions in the range from 83 to 923 K. Using experimental data on thermal diffusivity, heat capacity, and density, an equation for the dependence describing the change in thermal conductivity of the material under study in the range from 299 to 1273 K was obtained. It was revealed that ceramics produced from InFeZnO₄ nanoparticles obtained by the polymer-salt method have a higher thermal conductivity compared to those synthesized by standard ceramic technology from a mixture of In₂O₃, Fe₂O₃ and ZnO oxides. The results obtained allow us to recommend InFeZnO₄ as a basis for the creation of thermally stable functional materials with low thermal conductivity at high temperatures.

Cyclic trinuclear silver(I) complex, [AgPz]₃ (Pz = 3,5-bis(trifluoromethyl)pyrazolate), serves as a versatile platform for interaction with N^N-donor chelating aromatic ligands. In this study, pyrazolyl-1H-pyridine derivatives were proposed as ligands of this type, including 2-(3-phenyl-1H-pyrazole-5-yl)pyridine (L¹) and 2-methyl-6-(3-phenyl-1H-pyrazole-5-yl)pyridine (L²). It was found that a complexes of the composition [AgPzL₁]_n (1 : 1 : 1), regardless of the stoichiometry of the reactants, form in solution. When the resulting compounds are crystallized from toluene, binuclear complexes with the composition [AgPz₂Ln]₂ per one solvent molecule are formed. The formation of these structures is attributed to the formation of hydrogen bonds between the NH groups of pyrazole-pyridine (Lⁿ) and the unshared electron pairs of the nitrogen atoms of the pyrazolate ligands. Shortened Ag…Ag contacts (3.143-3.197 Å) are observed in the complex, leading to additional stabilization of the structure. As a result, the compounds exhibit ligand-centered phosphorescence in the solid state at room temperature.

The interaction of thallium(I) N,N-dipropyldithiocarbamate with [AuCl₄]^– anions in a 2M HCl medium was studied. The heterogeneous reaction of gold(III) binding from solution to the solid phase, including the red-ox process, results in the formation of a double dithiocarbamato-chlorido complex of [Au(S₂CNPr₂)₂][TlCl₄]. The crystals of the obtained compound are characterized by their ability to polymorphism: at 220 K the complex exists in the form of the α-modification (α-I), while at 296 K the β-modification (β-I) is stable. The α-I/β-I structures include 4/2 nonequivalent square-planar cations of [Au(S₂CNPr₂)₂]⁺ (A, 2 B, C/A, B) and 2/1 distorted tetrahedral anions [TlCl₄]^–. Self-assembly of these structural units, which are combined due to interionic secondary interactions (the most important of which are chalcogen bonds S···Cl), leads to the formation of the complicated supramolecular architectures such as cation-anionic pseudo-polymeric ribbons. Alternating along the edges of these ribbons and acting as double linkers, thallium(III) anions pairwise combine neighboring isomeric complex cations of [Au(S₂CNPr₂)₂]⁺, which are localized in the central part of the ribbons. When studying the thermal behavior of the complex, TlCl and elemental gold were identified as individual thermolysis products, which are quantitatively reduced and crystallized under low-temperature conditions (up to 300°C).

In the paper, compound with composition Bi_1.3Yb_0.7O₃ was prepared by solid state reactions. It was shown that compound had cubic structure, space group Fm3m, lattice parameter a = 0.54202 nm. The dissolution enthalpy of compound Bi_1.3Yb_0.7O₃ was measured by solution calorimetry in 2 M HCl and was ∆_solH⁰ = −227.8 ± 6.3 kJ mol⁻¹. Based on measured enthalpy of dissolution, the standard formation enthalpy of Bi_1.3Yb_0.7O₃ was calculated as following value: ∆_fH⁰ = −996.0 ± 7.9 kJ mol ⁻¹. Using Born-Haber cycle, the lattice enthalpy for Bi_1.3Yb_0.7O₃ was calculated: ∆_latH⁰ = −13278 kJ mol⁻¹.

Vanadium(V) oxide films doped with 10 mol% NiO and 10 mol. % WO₃ were obtained by aerosol printing. In the first case, the film crystallizes in tetragonal β-V₂O₅ modification with high texturing along the {200} crystallographic plane, while the material is X-ray amorphous when doped with tungsten. At nickel doping the film is formed by one-dimensional structures, while in the case of the sample V₂O₅–10 mol. % WO₃ — by particles of irregular shape or close to rounded. The values of electron yield work from the surface of the materials indicate high defectivity of the film containing WO₃. Both samples demonstrate anodic electrochromism, but V₂O₅–10 mol. % NiO is characterized by higher values of optical contrast and coloring efficiency. The results of the study clearly reflect the influence of the nature of the considered dopants on the functional properties of the obtained materials and demonstrate the promising potential of the aerosol printing method for the formation of electrochromic films.