Poly(vinyl chloride)/Nanocarbon Composites for Advanced Potentiometric Membrane Sensor Design.

Polymer nanocomposites filled with carbon nanoparticles (CNPs) are a hot topic in materials science. This article discusses the current research on the use of these materials as interfacial electron transfer films for solid contact potentiometric membrane sensors (SC-PMSs). The results of a comparative study of plasticized poly (vinyl chloride) (pPVC) matrices modified with single-walled carbon nanotubes (SWCNTs), fullerenes-C60, and their hybrid ensemble (SWCNTs-C60) are reported. The morphological characteristics and electrical conductivity of the prepared nanostructured composite films are reported. It was found that the specific electrical conductivity of the pPVC/SWCNTs-C60 polymer film was higher than that of pPVC filled with individual nanocomponents. The effectiveness of this composite material as an electron transfer film in a new potentiometric membrane sensor for detecting phenylpyruvic acid (in anionic form) was demonstrated. Screening for this metabolic product of phenylalanine in body fluids is of significant diagnostic interest in phenylketonuria (dementia), viral hepatitis, and alcoholism. The developed sensor showed a stable and fast Nernstian response for phenylpyruvate ions in aqueous solutions over the wide linear concentration range of 5 × 10-7-1 × 10-3 M, with a detection limit of 10-7.2 M.

Synthesis and Structures of Lead(II) Complexes with Substituted Derivatives of the Closo-Decaborate Anion with a Pendant N3 Group.

In this work, we studied lead(II) and cobalt(II) complexation of derivatives [2-B10H9O(CH2)2O(CH2)2N3]2- and [2-B10H9O(CH2)5N3]2- of the closo-decaborate anion containing pendant azido groups in the presence of 1,10-phenanthroline and 2,2'-bipyridyl. Mononuclear [PbL2{An}] and binuclear [Pb2L4(NO3)2{An}] lead complexes (where {An} is the N3-substituted boron cluster) were isolated and studied by IR spectroscopy and elemental analysis. The mononuclear lead(II) complex [Pb(phen)2[B10H9O(CH2)2O(CH2)2N3] and the binuclear lead(II) complex [Pb2(phen)4(NO3)2[B10H9O(CH2)5)N3] were determined by single-crystal X-ray diffraction. In complex [Pb2(phen)4(NO3)2[B10H9O(CH2)5)N3], the boron cluster is coordinated by the metal atom only via the 3c2e MHB bonds. In complex [Pb(phen)2[B10H9O(CH2)2O(CH2)2N3], the coordination environment of the metal includes BH groups of the boron cluster and the oxygen atom of the exo-polyhedral substituent. When the reaction was performed in a CH3CN/water mixture, the binuclear lead(II) complex [(Pb(bipy)NO3)(Pb(bipy)2NO3)(B10H9O(CH2)2O(CH2)2N3)]·CH3CN·H2O was isolated, where the boron cluster acts as a bridging ligand between lead atoms coordinated by the boron cage via the O atoms of the substituent and/or the BH groups. In the course of cobalt(II) complexation, the starting compound (Ph4P)2[B10H9O(CH2)5N3] was isolated and its structure was also determined by X-ray diffraction. Although a number of lead(II) complexes with coordinated N3 are known from the literature, no complexes with the boron cluster coordinated by the pendant N3 group involved in the metal coordination have been isolated.

Oxidation of Ceramic Materials Based on HfB2-SiC under the Influence of Supersonic CO2 Jets and Additional Laser Heating.

The features of oxidation of ultra-high-temperature ceramic material HfB2-30 vol.%SiC modified with 1 vol.% graphene as a result of supersonic flow of dissociated CO2 (generated with the use of high-frequency induction plasmatron), as well as under the influence of combined heating by high-speed CO2 jets and ytterbium laser radiation, were studied for the first time. It was found that the addition of laser radiation leads to local heating of the central region from ~1750 to ~2000-2200 °C; the observed temperature difference between the central region and the periphery of ~300-550 °C did not lead to cracking and destruction of the sample. Oxidized surfaces and cross sections of HfB2-SiC-CG ceramics with and without laser heating were investigated using X-ray phase analysis, Raman spectroscopy and scanning electron microscopy with local elemental analysis. During oxidation by supersonic flow of dissociated CO2, a multilayer near-surface region similar to that formed under the influence of high-speed dissociated air flows was formed. An increase in surface temperature with the addition of laser heating from 1750-1790 to 2000-2200 °C (short term, within 2 min) led to a two to threefold increase in the thickness of the degraded near-surface area of ceramics from 165 to 380 microns. The experimental results indicate promising applications of ceramic materials based on HfB2-SiC as part of high-speed flying vehicles in planetary atmospheres predominantly composed of CO2 (e.g., Venus and Mars).

Composites and Materials Prepared from Boron Cluster Anions and Carboranes.

Here, we present composites and materials that can be prepared starting with boron hydride cluster compounds (decaborane, decahydro-closo-decaborate and dodecahydro-closo-dodecaborate anions and carboranes). Recent examples of their utilization as boron protective coatings including using them to synthesize boron carbide, boron nitride, metal borides, metal-containing composites, and neutron shielding materials are discussed. The data are generalized demonstrate the versatile application of materials based on boron cluster anions and carboranes in various fields.

Current Trends and Promising Electrode Materials in Micro-Supercapacitor Printing.

The development of scientific and technological foundations for the creation of high-performance energy storage devices is becoming increasingly important due to the rapid development of microelectronics, including flexible and wearable microelectronics. Supercapacitors are indispensable devices for the power supply of systems requiring high power, high charging-discharging rates, cyclic stability, and long service life and a wide range of operating temperatures (from -40 to 70 °C). The use of printing technologies gives an opportunity to move the production of such devices to a new level due to the possibility of the automated formation of micro-supercapacitors (including flexible, stretchable, wearable) with the required type of geometric implementation, to reduce time and labour costs for their creation, and to expand the prospects of their commercialization and widespread use. Within the framework of this review, we have focused on the consideration of the key commonly used supercapacitor electrode materials and highlighted examples of their successful printing in the process of assembling miniature energy storage devices.

Hydrothermal Synthesis of a Cellular NiO Film on Carbon Paper as a Promising Way to Obtain a Hierarchically Organized Electrode for a Flexible Supercapacitor.

The formation of a cellular hierarchically organized NiO film on a carbon paper substrate under hydrothermal conditions using triethanolamine as a base has been studied. The thermal behavior of the carbon paper substrate with the applied semi-product shell was studied using synchronous thermal analysis (TGA/DSC) and it was demonstrated that such modification of the material surface leads to a noticeable increase in its thermal stability. Using scanning electron microscopy (SEM), it was shown that the NiO film grown on the carbon fiber surface is characterized by a complex cellular morphology, organized by partially layered individual nanosheets of about 4-5 nm thickness and lateral dimensions up to 1-2 µm, some edges and folds of which are located vertically relative to the carbon fiber surface. The surface of the obtained material was also examined using atomic force microscopy (AFM), and the electronic work function of the oxide shell surface was evaluated using the Kelvin probe force microscopy (KPFM) method. The electrochemical parameters of the obtained flexible NiO/CP electrode were analyzed: the dependence of the specific capacitance on the current density was determined and the stability of the material during cycling was studied, which showed that the proposed approach is promising for manufacturing hierarchically organized electrodes for flexible supercapacitors.

Low Temperature Chemoresistive Oxygen Sensors Based on Titanium-Containing Ti2CTx and Ti3C2Tx MXenes.

The chemoresistive properties of multilayer titanium-containing Ti2CTx and Ti3C2Tx MXenes, synthesized by etching the corresponding MAX phases with NaF solution in hydrochloric acid, and the composites based on them, obtained by partial oxidation directly in a sensor cell in an air flow at 150 °C, were studied. Significant differences were observed for the initial MXenes, both in microstructure and in the composition of surface functional groups, as well as in gas sensitivity. For single Ti2CTx and Ti3C2Tx MXenes, significant responses to oxygen and ammonia were observed. For their partial oxidation at a moderate temperature of 150 °C, a high humidity sensitivity (T, RH = 55%) is observed for Ti2CTx and a high and selective response to oxygen for Ti3C2Tx at 125 °C (RH = 0%). Overall, these titanium-containing MXenes and composites based on them are considered promising as receptor materials for low temperature oxygen sensors.

Gas-Sensitive Properties of ZnO/Ti2CTx Nanocomposites.

At present, a new class of 2D nanomaterials, MXenes, is of great scientific and applied interest, and their application prospects are very broad, including as effective doping components for receptor materials of MOS sensors. In this work we have studied the influence on the gas-sensitive properties of nanocrystalline zinc oxide synthesized by atmospheric pressure solvothermal synthesis, with the addition of 1-5% of multilayer two-dimensional titanium carbide Ti2CTx, obtained by etching Ti2AlC with NaF solution in hydrochloric acid. It was found that all the obtained materials have high sensitivity and selectivity with respect to 4-20 ppm NO2 at a detection temperature of 200 °C. It is shown that the selectivity towards this compound is best for the sample containing the highest amount of Ti2CTx dopant. It has been found that as the MXene content increases, there is an increase in nitrogen dioxide (4 ppm) from 1.6 (ZnO) to 20.5 (ZnO-5 mol% Ti2CTx). reactions which the responses to nitrogen dioxide increase. This may be due to the increase in the specific surface area of the receptor layers, the presence of MXene surface functional groups, as well as the formation of the Schottky barrier at the interface between the phases of the components.

Microplotter Printing of a Miniature Flexible Supercapacitor Electrode Based on Hierarchically Organized NiCo2O4 Nanostructures.

The hydrothermal synthesis of a nanosized NiCo2O4 oxide with several levels of hierarchical self-organization was studied. Using X-ray diffraction analysis (XRD) and Fourier-transform infrared (FTIR) spectroscopy, it was determined that under the selected synthesis conditions, a nickel-cobalt carbonate hydroxide hydrate of the composition M(CO3)0.5(OH)·0.11H2O (where M-Ni2+ and Co2+) is formed as a semi-product. The conditions of semi-product transformation into the target oxide were determined by simultaneous thermal analysis. It was found by means of scanning electron microscopy (SEM) that the main powder fraction consists of hierarchically organized microspheres of 3-10 µm in diameter, and individual nanorods are observed as the second fraction of the powder. Nanorod microstructure was further studied by transmission electron microscopy (TEM). A hierarchically organized NiCo2O4 film was printed on the surface of a flexible carbon paper (CP) using an optimized microplotter printing technique and functional inks based on the obtained oxide powder. It was shown by XRD, TEM, and atomic force microscopy (AFM) that the crystalline structure and microstructural features of the oxide particles are preserved when deposited on the surface of the flexible substrate. It was found that the obtained electrode sample is characterized by a specific capacitance value of 420 F/g at a current density of 1 A/g, and the capacitance loss during 2000 charge-discharge cycles at 10 A/g is 10%, which indicates a high material stability. It was established that the proposed synthesis and printing technology enables the efficient automated formation of corresponding miniature electrode nanostructures as promising components for flexible planar supercapacitors.

Obtaining of ZnO/Fe2O3 Thin Nanostructured Films by AACVD for Detection of ppb-Concentrations of NO2 as a Biomarker of Lung Infections.

ZnO/Fe2O3 nanocomposites with different concentration and thickness of the Fe2O3 layer were obtained by two-stage aerosol vapor deposition (AACVD). It was shown that the ZnO particles have a wurtzite structure with an average size of 51-66 nm, and the iron oxide particles on the ZnO surface have a hematite structure and an average size of 23-28 nm. According to EDX data, the iron content in the films was found to be 1.3-5.8 at.%. The optical properties of the obtained films were studied, and the optical band gap was found to be 3.16-3.26 eV. Gas-sensitive properties at 150-300 °C were studied using a wide group of analyte gases: CO, NH3, H2, CH4, C6H6, ethanol, acetone, and NO2. A high response to 100 ppm acetone and ethanol at 225-300 °C and a high and selective response to 300-2000 ppb NO2 at 175 °C were established. The effect of humidity on the magnitude and shape of the signal obtained upon NO2 detection was studied.

Hydrothermal Synthesis of Nickel Oxide and Its Application in the Additive Manufacturing of Planar Nanostructures.

The hydrothermal synthesis of nickel oxide in the presence of triethanolamine was studied. Furthermore, the relationship between the synthesis conditions, thermal behavior, crystal structure features, phase composition and microstructure of semi-products, and the target oxide nanopowders was established. The thermal behavior of the semi-products was studied using a simultaneous thermal analysis (in particular, using one that involved thermogravimetric analysis and differential scanning calorimetry, TGA/DSC). An X-ray diffraction (XRD) analysis revealed that varying the triethanolamine and nickel chloride concentration in the reaction system can govern the formation of α- and ß-Ni(OH)2-based semi-products that contain Ni(HCO3)2 or Ni2(CO3)(OH)2 as additional components. The set of functional groups in the powders was determined using a Fourier-transform infrared (FTIR) spectroscopy analysis. Using microextrusion printing, a composite NiO-(CeO2)0.80(Sm2O3)0.20 anode film was fabricated. Using XRD, scanning electron microscopy (SEM), and atomic force microscopy (AFM) analyses, it was demonstrated that the crystal structure, dispersity, and microstructure character of the obtained material correspond to the initial nanopowders. Using Kelvin probe force microscopy (KPFM) and scanning capacitance microscopy (SCM), the local electrophysical properties of the printed composite film were examined. The value of its conductivity was evaluated using the four-probe method on a direct current in the temperature range of 300-650 °C. The activation energy for the 500-650 °C region, which is of most interest in the context of intermediate-temperature SOFCs working temperatures, has been estimated.

Application of Titanium Carbide MXenes in Chemiresistive Gas Sensors.

The titanium carbide MXenes currently attract an extreme amount of interest from the material science community due to their promising functional properties arising from the two-dimensionality of these layered structures. In particular, the interaction between MXene and gaseous molecules, even at the physisorption level, yields a substantial shift in electrical parameters, which makes it possible to design gas sensors working at RT as a prerequisite to low-powered detection units. Herein, we consider to review such sensors, primarily based on Ti3C2Tx and Ti2CTx crystals as the most studied ones to date, delivering a chemiresistive type of signal. We analyze the ways reported in the literature to modify these 2D nanomaterials for (i) detecting various analyte gases, (ii) improving stability and sensitivity, (iii) reducing response/recovery times, and (iv) advancing a sensitivity to atmospheric humidity. The most powerful approach based on designing hetero-layers of MXenes with other crystals is discussed with regard to employing semiconductor metal oxides and chalcogenides, noble metal nanoparticles, carbon materials (graphene and nanotubes), and polymeric components. The current concepts on the detection mechanisms of MXenes and their hetero-composites are considered, and the background reasons for improving gas-sensing functionality in the hetero-composite when compared with pristine MXenes are classified. We formulate state-of-the-art advances and challenges in the field while proposing some possible solutions, in particular via employing a multisensor array paradigm.

Synthesis of Disubstituted Carboxonium Derivatives of Closo-Decaborate Anion [2,6-B10H8O2CC6H5]-: Theoretical and Experimental Study.

A comprehensive study focused on the preparation of disubstituted carboxonium derivatives of closo-decaborate anion [2,6-B10H8O2CC6H5]- was carried out. The proposed synthesis of the target product was based on the interaction between the anion [B10H11]- and benzoic acid C6H5COOH. It was shown that the formation of this product proceeds stepwise through the formation of a mono-substituted product [B10H9OC(OH)C6H5]-. In addition, an alternative one-step approach for obtaining the target derivative is postulated. The structure of tetrabutylammonium salts of carboxonium derivative ((C4H9)4N)[2,6-B10H8O2CC6H5] was established with the help of X-ray structure analysis. The reaction pathway for the formation of [2,6-B10H8O2CC6H5]- was investigated with the help of density functional theory (DFT) calculations. This process has an electrophile induced nucleophilic substitution (EINS) mechanism, and intermediate anionic species play a key role. Such intermediates have a structure in which one boron atom coordinates two hydrogen atoms. The regioselectivity for the process of formation for the 2,6-isomer was also proved by theoretical calculations. Generally, in the experimental part, the simple and available approach for producing disubstituted carboxonium derivative was introduced, and the mechanism of this process was investigated with the help of theoretical calculations. The proposed approach can be applicable for the preparation of a wide range of disubstituted derivatives of closo-borate anions.

A New Approach to the Synthesis of Nanocrystalline Cobalt Boride in the Course of the Thermal Decomposition of Cobalt Complexes [Co(DMF)6]2+ with Boron Cluster Anions.

In the course of the study, nanocrystalline cobalt monoboride was prepared by thermal decomposition of precursors [Co(DMF)6][An], where [An] = [B12H12]2- (1), [trans-B20H18]2- (2) or [B10Cl10]2- (3) in an argon atmosphere. Three new salt-like compounds 1-3 were prepared when Co(NO3)2 was allowed to react with (Et3NH)2[An]. Compound 1 is new; the structures of compounds 2 and 3 have been previously reported. Samples 1-3 were annealed at 900 °C in argon to form samples 1a-3a, which were characterized by single crystal XRD for 1 and powder XRD for 1-3. Powder XRD on the products showed the formation of BN and CoB for 1a in a 1:1 ratio; 2a gave a higher CoB:BN ratio but an overall decreased crystallinity. For 3a, only CoB was found. IR spectra of samples 1a-3a as well as X-ray spectral fluorescence analysis for 3a confirmed these results. The nanoparticular character of the decomposition products 1a-3a was shown using TEM; quite small particle sizes of about 10-15 nm and a quite normal size distribution were found for 1a and 2a, while the decomposition of 3 gave large particles with 200-350 nm and a broad distribution.

Synthesis of ((CeO2)0.8(Sm2O3)0.2)@NiO Core-Shell Type Nanostructures and Microextrusion Printing of a Composite Anode Based on Them.

The process of the hydrothermal synthesis of hierarchically organized nanomaterials with the core-shell structure with the composition ((CeO2)0.8(Sm2O3)0.2)@NiO was studied, and the prospects for their application in the formation of planar composite structures using microextrusion printing were shown. The hydrothermal synthesis conditions of the (CeO2)0.8(Sm2O3)0.2 nanospheres were determined, and the approach to their surface modification by growing the NiO shell with the formation of core-shell structures equally distributed between the larger nickel(II) oxide nanosheets was developed. The resulting nanopowder was used as a functional ink component in the microextrusion printing of the corresponding composite coating. The microstructure of the powders and the oxide coating was studied by scanning (SEM) and transmission electron microscopy (TEM), the crystal structure was explored by X-ray diffraction analysis (XRD), the set of functional groups in the powders was studied by Fourier-transform infrared spectroscopy (FTIR) spectroscopy, and their thermal behavior in an air flow by synchronous thermal analysis (TGA/DSC). The electronic state of the chemical elements in the resulting coating was studied using X-ray photoelectron spectroscopy (XPS). The surface topography and local electrophysical properties of the composite coating were studied using atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). Using impedance spectroscopy, the temperature dependence of the specific electrical conductivity of the obtained composite coating was estimated.

Atmospheric Pressure Solvothermal Synthesis of Nanoscale SnO2 and Its Application in Microextrusion Printing of a Thick-Film Chemosensor Material for Effective Ethanol Detection.

The atmospheric pressure solvothermal (APS) synthesis of nanocrystalline SnO2 (average size of coherent scattering regions (CSR)-7.5 ± 0.6 nm) using tin acetylacetonate as a precursor was studied. The resulting nanopowder was used as a functional ink component in microextrusion printing of a tin dioxide thick film on the surface of a Pt/Al2O3/Pt chip. Synchronous thermal analysis shows that the resulting semiproduct is transformed completely into tin dioxide nanopowder at 400 °C within 1 h. The SnO2 powder and the resulting film were shown to have a cassiterite-type structure according to X-ray diffraction analysis, and IR spectroscopy was used to establish the set of functional groups in the material composition. The microstructural features of the tin dioxide powder were analyzed using scanning (SEM) and transmission (TEM) electron microscopy: the average size of the oxide powder particles was 8.2 ± 0.7 nm. Various atomic force microscopy (AFM) techniques were employed to investigate the topography of the oxide film and to build maps of surface capacitance and potential distribution. The temperature dependence of the electrical conductivity of the printed SnO2 film was studied using impedance spectroscopy. The chemosensory properties of the formed material when detecting H2, CO, NH3, C6H6, C3H6O and C2H5OH, including at varying humidity, were also examined. It was demonstrated that the obtained SnO2 film has an increased sensitivity (the sensory response value was 1.4-63.5) and selectivity for detection of 4-100 ppm C2H5OH at an operating temperature of 200 °C.

Investigation of the Effect of Supersonic Flow of Dissociated Nitrogen on ZrB2-HfB2-SiC Ceramics Doped with 10 vol.% Carbon Nanotubes.

The method of fabricating dense ultra-high temperature ceramic materials ZrB2−HfB2−SiC−CCNT was developed using a combination of sol-gel synthesis and reaction hot pressing approaches at 1800 °C. It was found that the introduction of multilayer nanotubes (10 vol.%) led to an increase in the consolidation efficiency of ceramics (at temperatures > 1600 °C). The obtained ZrB2−HfB2−SiC and ZrB2−HfB2−SiC−CCNT materials were characterized by a complex of physical and chemical analysis methods. A study of the effects on the modified sample ZrB2−HfB2−SiC−CCNT composition speed flow of partially dissociated nitrogen, using a high-frequency plasmatron, showed that, despite the relatively low temperature established on the surface (≤1585 °C), there was a significant change in the chemical composition and surface microstructure: in the near-surface layer, zirconium−hafnium carbonitride, amorphous boron nitride, and carbon were present. The latter caused changes in crucial characteristics such as the emission coefficient and surface catalyticity.

Microextrusion Printing of Hierarchically Structured Thick V2O5 Film with Independent from Humidity Sensing Response to Benzene.

The process of V2O5 oxide by the combination of sol-gel technique and hydrothermal treatment using heteroligand [VO(C5H7O2)2-x(C4H9O)x] precursor was studied. Using thermal analysis, X-ray powder diffraction (XRD) and infra-red spectroscopy (IR), it was found that the resulting product was VO2(B), which after calcining at 300 °C (1 h), oxidized to orthorhombic V2O5. Scanning electron microscopy (SEM) results for V2O5 powder showed that it consisted of nanosheets (~50 nm long and ~10 nm thick) assembled in slightly spherical hierarchic structures (diameter ~200 nm). VO2 powder dispersion was used as functional ink for microextrusion printing of oxide film. After calcining the film at 300 °C (30 min), it was found that it oxidized to V2O5, with SEM and atomic force microscopy (AFM) results showing that the film structure retained the hierarchic structure of the powder. Using Kelvin probe force microscopy (KPFM), the work function value for V2O5 film in ambient conditions was calculated (4.81 eV), indicating a high amount of deficiencies in the sample. V2O5 film exhibited selective response upon sensing benzene, with response value invariable under changing humidity. Studies of the electrical conductivity of the film revealed increased resistance due to high film porosity, with conductivity activation energy being 0.26 eV.

Non-Covalent Interactions in the Crystal Structures of Perbrominated Sulfonium Derivatives of the closo-Decaborate Anion.

A new series of compounds based on perbrominated disubstituted sulfonium derivatives of the closo-decaborate anion (n-Bu4N)[2-B10Br9SR2] (R = n-Pr, i-Pr, n-Bu, n-C8H17, n-C12H25, n-C18H37) was obtained, characterised by modern physicochemical methods of analysis. According to the results of an X-ray diffraction study, some of the anions and solvate molecules were disordered. The cations (n-Bu4N)+ and anions [2-B10Br9SR2]- were associated via C-H…Br and H…H contacts. In addition, Br…Br interactions between anions were revealed. The role of these contacts was analysed in terms of Hirshfeld surface analysis, QTAIM theory and the NCI method using quantum chemical calculations. An increase in the size of the alkyl R moiety led to significant strengthening of the total energy of H…H interactions. In the case of R = -n-C18H37, a parallel mutual orientation of alkyl moieties was established that was similar to the packing of salts of fatty acids. The nature of C-H…Br and Br…Br interionic interactions was found to be attractive, in contrast to the repulsive nature of intermolecular Br…Br interactions.

High-Temperature Spin Crossover in Iron(II) Complexes with 2,6-Bis(1H-imidazol-2-yl)pyridine.

Novel iron(II) coordination compounds containing a ligand 2,6-bis(1H-imidazol-2-yl)pyridine (L), having such a composition as [FeL2]SO4·0.5H2O, [FeL2]Br2·H2O, [FeL2](ReO4)2, [FeL2]B10H10∙H2O, [FeL2]B12H12∙1.5H2O had been synthesized and studied using UV-Vis (diffuse reflectance), infrared, extended X-ray absorption fine structure (EXAFS), and Mössbauer spectroscopy methods, as well as X-ray diffraction and static magnetic susceptibility methods. The analysis of the µeff(T) dependence in the temperature range of 80-600 K have shown that all the obtained complexes exhibit a high-temperature spin crossover 1A1 ↔ 5T2.