Pub Date : 2024-09-15DOI: 10.1134/s0036023624601648
A. V. Gerasimenko, T. F. Antokhina, N. N. Savchenko
Abstract
Compound Rb3(SbF3)(Zr2F11)·0.5H2O and its dehydration product Rb3(SbF3)(Zr2F11) were synthesized and their structures were studied. It was found that compound Rb3(SbF3)(Zr2F11)·0.5H2O has a unique fluoride zirconate framework structure built of ring tetrameric fragments (Zr4F24) connected to each other at the vertices by bridging fluorine atoms. Inside the tetrameric fragments, ZrF8 polyhedra are connected to each other along common edges. The zirconium framework [Zr2F11]3– is bound by Zr–F–Sb fluoride bridges from the second coordination sphere of antimony atoms. The structure of the dehydrated compound Rb3(SbF3)(Zr2F11) is a three-dimensional framework consisting of infinite chains of composition [Zr2F11]3–. The chains are formed by ZrF7 polyhedra connected along edges and vertices and united with each other into a three-dimensional framework by fluoride bridges Zr–F–Sb from the second coordination sphere of antimony atoms. In Rb3(SbF3)(Zr2F11), in the temperature range 247–256 K, a reversible phase transition occurs from the partially disordered high-temperature phase α to the ordered low-temperature phase β. With the participation of fluorine atoms of the second coordination sphere and a lone pair of electrons around antimony atoms, coordination polyhedra are formed in the structures in the form of distorted (SbEF5) and single-capped (SbEF6) octahedra.
{"title":"Structural Organization and Thermal Behavior of Compounds Rb3(SbF3)(Zr2F11)·0.5H2O and Rb3(SbF3)(Zr2F11)","authors":"A. V. Gerasimenko, T. F. Antokhina, N. N. Savchenko","doi":"10.1134/s0036023624601648","DOIUrl":"https://doi.org/10.1134/s0036023624601648","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Compound Rb<sub>3</sub>(SbF<sub>3</sub>)(Zr<sub>2</sub>F<sub>11</sub>)·0.5H<sub>2</sub>O and its dehydration product Rb<sub>3</sub>(SbF<sub>3</sub>)(Zr<sub>2</sub>F<sub>11</sub>) were synthesized and their structures were studied. It was found that compound Rb<sub>3</sub>(SbF<sub>3</sub>)(Zr<sub>2</sub>F<sub>11</sub>)·0.5H<sub>2</sub>O has a unique fluoride zirconate framework structure built of ring tetrameric fragments (Zr<sub>4</sub>F<sub>24</sub>) connected to each other at the vertices by bridging fluorine atoms. Inside the tetrameric fragments, ZrF<sub>8</sub> polyhedra are connected to each other along common edges. The zirconium framework [Zr<sub>2</sub>F<sub>11</sub>]<sup>3–</sup> is bound by Zr–F–Sb fluoride bridges from the second coordination sphere of antimony atoms. The structure of the dehydrated compound Rb<sub>3</sub>(SbF<sub>3</sub>)(Zr<sub>2</sub>F<sub>11</sub>) is a three-dimensional framework consisting of infinite chains of composition [Zr<sub>2</sub>F<sub>11</sub>]<sup>3–</sup>. The chains are formed by ZrF<sub>7</sub> polyhedra connected along edges and vertices and united with each other into a three-dimensional framework by fluoride bridges Zr–F–Sb from the second coordination sphere of antimony atoms. In Rb<sub>3</sub>(SbF<sub>3</sub>)(Zr<sub>2</sub>F<sub>11</sub>), in the temperature range 247–256 K, a reversible phase transition occurs from the partially disordered high-temperature phase α to the ordered low-temperature phase β. With the participation of fluorine atoms of the second coordination sphere and a lone pair of electrons around antimony atoms, coordination polyhedra are formed in the structures in the form of distorted (SbEF<sub>5</sub>) and single-capped (SbEF<sub>6</sub>) octahedra.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142251747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-15DOI: 10.1134/s0036023624601958
L. T. Denisova, D. V. Belokopytova, Yu. F. Kargin, G. V. Vasil’ev, N. V. Belousova, V. M. Denisov
Abstract
Germanates CaYb2Ge4O12 and CaLu2Ge4O12 have been prepared via firing the solid precursor oxides CaO, Yb2O3 (Lu2O3), and GeO2 in air at 1223–1423 K. The X-ray diffraction crystal structures of the prepared germanates have been determined. The high-temperature heat capacity in the range 320–1050 K has been measured by differential scanning calorimetry (DSC). The measured heat capacities are well fitted by the Maier–Kelley equation: Cp(CaYb2Ge4O12) = (left( {{{416}}{{.4; pm ;0}}{{.40}}} right) + left( {{{72}}{{.67; pm ;2}}{{.30}}} right){{ times 1}}{{{{0}}}^{{{{-3}}}}}T - left( {{{50}}{{.13; pm ;0}}{{.19}}} right){{ times 1}}{{{{0}}}^{{{5}}}}{{T}^{{{{-2}}}}}), and Cp(CaLu2Ge4O12) = (left( {{{450}}{{.0; pm ;1}}{{.75}}} right) + left( {{{15}}{{.46; pm ;1}}{{.90}}} right){{ times 1}}{{{{0}}}^{{{{-3}}}}}T - left( {{{78}}{{.67; pm ;1}}{{.60}}} right){{ times 1}}{{{{0}}}^{{{5}}}}{{T}^{{{{-2}}}}}). These results have been used to calculate selected thermodynamic properties of the prepared germanates.
摘要 通过在 1223-1423 K 的空气中焙烧固体前体氧化物 CaO、Yb2O3 (Lu2O3) 和 GeO2，制备了锗酸盐 CaYb2Ge4O12 和 CaLu2Ge4O12。通过差示扫描量热法（DSC）测量了 320-1050 K 范围内的高温热容量。测得的热容量与 Maier-Kelley 方程十分吻合：Cp(CaYb2Ge4O12) = left( {{{416}}{{.4; pm ;0}}{{.40}} right) + left( {{{72}}{{.67; pm ;2}}{{.30}} right){{ times 1}}{{{{0}}^{{{{-3}}}}}T - left( {{{50}}{{.13; pm ;0}}{{.19}}} right){{ times 1}}{{{{0}}}^{{5}}}}{{T}^{{{{-2}}}}}), and Cp(CaLu2Ge4O12) =(left( {{450}}{.0; pm ;1}}{{.75}} right) + left( {{{15}}{{.46; pm ;1}}{{.90}} right){{ times 1}{{{{0}}}^{{{{-3}}}}}T - left( {{{78}}{.67; pm;1}}{{.60}} right){{ times 1}}{{{{0}}}^{{5}}}}{T}^{{{{-2}}}}}).这些结果被用来计算所制备的锗酸盐的部分热力学性质。
{"title":"Synthesis and Thermodynamic Study of CaYb2Ge4O12 and CaLu2Ge4O12 Germanates in the Range 320–1050 K","authors":"L. T. Denisova, D. V. Belokopytova, Yu. F. Kargin, G. V. Vasil’ev, N. V. Belousova, V. M. Denisov","doi":"10.1134/s0036023624601958","DOIUrl":"https://doi.org/10.1134/s0036023624601958","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Germanates CaYb<sub>2</sub>Ge<sub>4</sub>O<sub>12</sub> and CaLu<sub>2</sub>Ge<sub>4</sub>O<sub>12</sub> have been prepared via firing the solid precursor oxides CaO, Yb<sub>2</sub>O<sub>3</sub> (Lu<sub>2</sub>O<sub>3</sub>), and GeO<sub>2</sub> in air at 1223–1423 K. The X-ray diffraction crystal structures of the prepared germanates have been determined. The high-temperature heat capacity in the range 320–1050 K has been measured by differential scanning calorimetry (DSC). The measured heat capacities are well fitted by the Maier–Kelley equation: <i>C</i><sub><i>p</i></sub>(CaYb<sub>2</sub>Ge<sub>4</sub>O<sub>12</sub>) = <span>(left( {{{416}}{{.4; pm ;0}}{{.40}}} right) + left( {{{72}}{{.67; pm ;2}}{{.30}}} right){{ times 1}}{{{{0}}}^{{{{-3}}}}}T - left( {{{50}}{{.13; pm ;0}}{{.19}}} right){{ times 1}}{{{{0}}}^{{{5}}}}{{T}^{{{{-2}}}}})</span>, and <i>C</i><sub><i>p</i></sub>(CaLu<sub>2</sub>Ge<sub>4</sub>O<sub>12</sub>) = <span>(left( {{{450}}{{.0; pm ;1}}{{.75}}} right) + left( {{{15}}{{.46; pm ;1}}{{.90}}} right){{ times 1}}{{{{0}}}^{{{{-3}}}}}T - left( {{{78}}{{.67; pm ;1}}{{.60}}} right){{ times 1}}{{{{0}}}^{{{5}}}}{{T}^{{{{-2}}}}})</span>. These results have been used to calculate selected thermodynamic properties of the prepared germanates.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"39 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142251749","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-15DOI: 10.1134/s003602362470058x
A. O. Borodin, E. Yu. Filatov, P. E. Plusnin, N. V. Kuratieva, S. V. Korenev, G. A. Kostin
Abstract
Procedures for the synthesis of new double complex salts [Cu(im)4][RuNOCl5], [Ni(im)6][RuNOCl5]·H2O, and p-[Ni(im)4(DMF)2][RuNOCl5] have been developed and their crystal structure have been determined. Thermal properties of the synthesized DCS have been studied under inert and reducing atmospheres using synchronous TG–DTA and ex situ XRD of intermediate and final thermolysis products. It has been found that thermal decomposition occurs in three stages. Thermolysis of [Cu(im)4][RuNOCl5] under inert and reducing atmospheres gives rise to the mixture of copper and ruthenium, while the thermal decomposition of [Ni(im)6][RuNOCl5]·H2O under an inert atmosphere results in a mixture of nickel and ruthenium. A supersaturated Ni0.27Ru0.73 solid solution can be obtained in the nickel-ruthenium system upon thermolysis under a reducing atmosphere at temperature up to 400°C. Increase in thermolysis temperature up to 800°C leads to the partial decomposition of the solid solution.
{"title":"New Double Complex Salts [M(im)n][RuNOCl5] (M = Ni, Cu): Synthesis, Structure, and Thermal Properties","authors":"A. O. Borodin, E. Yu. Filatov, P. E. Plusnin, N. V. Kuratieva, S. V. Korenev, G. A. Kostin","doi":"10.1134/s003602362470058x","DOIUrl":"https://doi.org/10.1134/s003602362470058x","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Procedures for the synthesis of new double complex salts [Cu(im)<sub>4</sub>][RuNOCl<sub>5</sub>], [Ni(im)<sub>6</sub>][RuNOCl<sub>5</sub>]·H<sub>2</sub>O, and <i>p</i>-[Ni(im)<sub>4</sub>(DMF)<sub>2</sub>][RuNOCl<sub>5</sub>] have been developed and their crystal structure have been determined. Thermal properties of the synthesized DCS have been studied under inert and reducing atmospheres using synchronous TG–DTA and ex situ XRD of intermediate and final thermolysis products. It has been found that thermal decomposition occurs in three stages. Thermolysis of [Cu(im)<sub>4</sub>][RuNOCl<sub>5</sub>] under inert and reducing atmospheres gives rise to the mixture of copper and ruthenium, while the thermal decomposition of [Ni(im)<sub>6</sub>][RuNOCl<sub>5</sub>]·H<sub>2</sub>O under an inert atmosphere results in a mixture of nickel and ruthenium. A supersaturated Ni<sub>0.27</sub>Ru<sub>0.73</sub> solid solution can be obtained in the nickel-ruthenium system upon thermolysis under a reducing atmosphere at temperature up to 400°C. Increase in thermolysis temperature up to 800°C leads to the partial decomposition of the solid solution.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"6 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142251744","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-15DOI: 10.1134/s0036023624601697
N. P. Simonenko, T. L. Simonenko, Ph. Yu. Gorobtsov, P. V. Arsenov, I. A. Volkov, E. P. Simonenko
Abstract
Polyol synthesis of thin silver nanowires has been studied and their suitability for the formation of transparent electrodes has been shown. The influence of stepwise heating of the reaction system on the position and shape of the absorption band associated with the surface plasmon resonance of the formed silver nanostructures has been determined. Using X-ray powder diffraction analysis, it has been found that the material does not contain crystalline impurities and has a face-centered cubic lattice. According to the scanning and transmission electron microscopy data, the main fraction is represented by elongated nanostructures with 10–15 μm length (however, there are also structures with length up to 20 μm) characteristic for silver nanowires of the arc-shaped type. It is shown that the Ag nanowires obtained are quite thin (diameter is about 35–45 nm). In addition, some amount of microrods of 1–3 µm length is observed in the composition of the material, the diameter of which grows from 70 to 150 nm with decreasing length. In smaller quantities there is also an admixture of zero-dimensional particles, which are polyhedrons of various complexity. Atomic force microscopy has been used to study the surface of the film based on the obtained silver nanowires and the diameter of individual nanowire has been estimated. The optical properties and surface resistivity of the films based on the obtained silver nanowires have been examined. It has been found that the increase in transmittance at 550 nm from 73.9 to 90.3% is accompanied by an increase in the resistance value from 25 to 146 Ω/sq.
{"title":"Polyol Synthesis of Silver Nanowires and Their Application for Transparent Electrode Fabrication","authors":"N. P. Simonenko, T. L. Simonenko, Ph. Yu. Gorobtsov, P. V. Arsenov, I. A. Volkov, E. P. Simonenko","doi":"10.1134/s0036023624601697","DOIUrl":"https://doi.org/10.1134/s0036023624601697","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Polyol synthesis of thin silver nanowires has been studied and their suitability for the formation of transparent electrodes has been shown. The influence of stepwise heating of the reaction system on the position and shape of the absorption band associated with the surface plasmon resonance of the formed silver nanostructures has been determined. Using X-ray powder diffraction analysis, it has been found that the material does not contain crystalline impurities and has a face-centered cubic lattice. According to the scanning and transmission electron microscopy data, the main fraction is represented by elongated nanostructures with 10–15 μm length (however, there are also structures with length up to 20 μm) characteristic for silver nanowires of the arc-shaped type. It is shown that the Ag nanowires obtained are quite thin (diameter is about 35–45 nm). In addition, some amount of microrods of 1–3 µm length is observed in the composition of the material, the diameter of which grows from 70 to 150 nm with decreasing length. In smaller quantities there is also an admixture of zero-dimensional particles, which are polyhedrons of various complexity. Atomic force microscopy has been used to study the surface of the film based on the obtained silver nanowires and the diameter of individual nanowire has been estimated. The optical properties and surface resistivity of the films based on the obtained silver nanowires have been examined. It has been found that the increase in transmittance at 550 nm from 73.9 to 90.3% is accompanied by an increase in the resistance value from 25 to 146 Ω/sq.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142251745","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-15DOI: 10.1134/s0036023624700566
P. N. D’yachkov, P. A. Kulyamin
Abstract
The band structure of single-walled SiC (n1, n2) nanotubes (n1 = 7, 0 ≤ n2 ≤ 7) as a function of spin and chirality has been calculated by the relativistic augmented cylindrical wave method. It has been found that the nanotubes are wide-band semiconductors with Eg ranging from 2.26 to 3.15 eV, and the spin–orbit splitting of the valence and conduction band edges are in the range 0.05–3.5 meV. The spin–orbit gap energies in righthanded and lefthanded enantiomers coincide, but the spins are opposite. Chiral nanotubes most suitable for selective spin transport with potentially high fluxes of α- and β-electrons in opposite directions have been determined.
{"title":"Spin Properties of Chiral SiC Nanotubes","authors":"P. N. D’yachkov, P. A. Kulyamin","doi":"10.1134/s0036023624700566","DOIUrl":"https://doi.org/10.1134/s0036023624700566","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>The band structure of single-walled SiC (<i>n</i><sub>1</sub>, <i>n</i><sub>2</sub>) nanotubes (<i>n</i><sub>1</sub> = 7, 0 ≤ <i>n</i><sub>2</sub> ≤ 7) as a function of spin and chirality has been calculated by the relativistic augmented cylindrical wave method. It has been found that the nanotubes are wide-band semiconductors with <i>E</i><sub><i>g</i></sub> ranging from 2.26 to 3.15 eV, and the spin–orbit splitting of the valence and conduction band edges are in the range 0.05–3.5 meV. The spin–orbit gap energies in righthanded and lefthanded enantiomers coincide, but the spins are opposite. Chiral nanotubes most suitable for selective spin transport with potentially high fluxes of α- and β-electrons in opposite directions have been determined.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"54 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142251746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-15DOI: 10.1134/s0036023624601703
E. P. Simonenko, A. S. Mokrushin, I. A. Nagornov, Yu. M. Gorban, T. L. Simonenko, N. P. Simonenko, N. T. Kuznetsov
Abstract
The method of modification of accordion-like complex Ti0.2V1.8CTx MXene with tin(IV) and vanadium oxides was developed based on hydrothermal synthesis of SnO2 in water-alcoholic medium in the presence of dispersed particles of two-dimensional vanadium-titanium carbide. Coating Ti0.2V1.8CTx-10 mol % SnO2 was deposited by microplotter printing on a specialized substrate followed by heat treatment in air at 300°С for 1 h. For the formed nanocomposite layer Ti0.2V1.8CTx–V2O5–SnO2, chemosensor properties were comprehensively studied for a number of analyte gases, including 100 ppm CO, NH3, NO2, benzene, acetone, ethanol, 1000 ppm H2, methane, and 10% oxygen. High sensitivity and selectivity of the nanocomposite at operating temperatures of 150 and 200°С to nitrogen dioxide were shown, the responses to 100 ppm NO2 were found to be 281 and 873%, respectively.
{"title":"Chemosensory Properties of Nanocomposite Ti0.2V1.8CTx–V2O5–SnO2","authors":"E. P. Simonenko, A. S. Mokrushin, I. A. Nagornov, Yu. M. Gorban, T. L. Simonenko, N. P. Simonenko, N. T. Kuznetsov","doi":"10.1134/s0036023624601703","DOIUrl":"https://doi.org/10.1134/s0036023624601703","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>The method of modification of accordion-like complex Ti<sub>0.2</sub>V<sub>1.8</sub>CT<sub><i>x</i></sub> MXene with tin(IV) and vanadium oxides was developed based on hydrothermal synthesis of SnO<sub>2</sub> in water-alcoholic medium in the presence of dispersed particles of two-dimensional vanadium-titanium carbide. Coating Ti<sub>0.2</sub>V<sub>1.8</sub>CT<sub><i>x</i></sub>-10 mol % SnO<sub>2</sub> was deposited by microplotter printing on a specialized substrate followed by heat treatment in air at 300°С for 1 h. For the formed nanocomposite layer Ti<sub>0.2</sub>V<sub>1.8</sub>CT<sub><i>x</i></sub>–V<sub>2</sub>O<sub>5</sub>–SnO<sub>2</sub>, chemosensor properties were comprehensively studied for a number of analyte gases, including 100 ppm CO, NH<sub>3</sub>, NO<sub>2</sub>, benzene, acetone, ethanol, 1000 ppm H<sub>2</sub>, methane, and 10% oxygen. High sensitivity and selectivity of the nanocomposite at operating temperatures of 150 and 200°С to nitrogen dioxide were shown, the responses to 100 ppm NO<sub>2</sub> were found to be 281 and 873%, respectively.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"39 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142251750","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-15DOI: 10.1134/s003602362460148x
A. V. Kolbunova, I. N. Klyukin, A. S. Kubasov, N. A. Selivanov, A. Yu. Bykov, A. P. Zhdanov, K. Yu. Zhizhin, N. T. Kuznetsov
Abstract
The series of carboxonium derivatives of the closo-decaborate anion of the general form [2,6-B10H8O2CC6H4R]–, where R = F, CH3, C3H7, and C6H5, were prepared. To obtain the target systems, the reaction between the [B10H11]– anion and aromatic carboxylic acids was used. This process took place in two stages through the formation of a monosubstituted derivative of the general form [2-B10H9OC(OH)C6H4R]–, where R = F, CH3, C3H7, and C6H5, followed by intramolecular cyclization, leading to the formation of the target disubstituted carboxonium derivatives. The structure of the [2,6-B10H8O2CC6H4-C6H5]– anion was determined by single-crystal X-ray diffraction. The resulting carboxonium derivatives are capable of protonation to form neutral systems of the general form [2,6-B10H8O2CC6H4R(Hfac)]0, where R = F, CH3, C3H7, C6H5. When a protonated carboxonium derivative of acetonitrile is added to a solution, a trisubstituted derivative of the general form [B10H7O2CC6H4R(NCCH3)]0 is formed.
摘要 本研究制备了一系列一般形式为[2,6-B10H8O2CC6H4R]-（其中 R = F、CH3、C3H7 和 C6H5）的闭癸酸阴离子羧鎓衍生物。为了获得目标体系，[B10H11]- 阴离子与芳香族羧酸发生了反应。这一过程分为两个阶段，首先形成通式为[2-B10H9OC(OH)C6H4R]-的单取代衍生物，其中 R = F、CH3、C3H7 和 C6H5，然后进行分子内环化，最终形成目标二取代羧基衍生物。通过单晶 X 射线衍射确定了 [2,6-B10H8O2CC6H4-C6H5]- 阴离子的结构。由此得到的羧鎓衍生物能够质子化，形成一般形式为 [2,6-B10H8O2CC6H4R(Hfac)]0 的中性体系，其中 R = F、CH3、C3H7、C6H5。当质子化的乙腈羧基衍生物加入溶液中时，会形成一般形式为[B10H7O2CC6H4R(NCCH3)]0 的三取代衍生物。
{"title":"Carboxonium Derivatives of closo-Decaborate Anion [2,6-B10H8O2CC6H4R]– Based on Aromatic Carboxylic Acids: Synthesis and Physicochemical Properties","authors":"A. V. Kolbunova, I. N. Klyukin, A. S. Kubasov, N. A. Selivanov, A. Yu. Bykov, A. P. Zhdanov, K. Yu. Zhizhin, N. T. Kuznetsov","doi":"10.1134/s003602362460148x","DOIUrl":"https://doi.org/10.1134/s003602362460148x","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>The series of carboxonium derivatives of the <i>closo</i>-decaborate anion of the general form [2,6-B<sub>10</sub>H<sub>8</sub>O<sub>2</sub>CC<sub>6</sub>H<sub>4</sub>R]<sup>–</sup>, where R = F, CH<sub>3</sub>, C<sub>3</sub>H<sub>7</sub>, and C<sub>6</sub>H<sub>5</sub>, were prepared. To obtain the target systems, the reaction between the [B<sub>10</sub>H<sub>11</sub>]<sup>–</sup> anion and aromatic carboxylic acids was used. This process took place in two stages through the formation of a monosubstituted derivative of the general form [2-B<sub>10</sub>H<sub>9</sub>OC(OH)C<sub>6</sub>H<sub>4</sub>R]<sup>–</sup>, where R = F, CH<sub>3</sub>, C<sub>3</sub>H<sub>7</sub>, and C<sub>6</sub>H<sub>5</sub>, followed by intramolecular cyclization, leading to the formation of the target disubstituted carboxonium derivatives. The structure of the [2,6-B<sub>10</sub>H<sub>8</sub>O<sub>2</sub>CC<sub>6</sub>H<sub>4</sub>-C<sub>6</sub>H<sub>5</sub>]<sup>–</sup> anion was determined by single-crystal X-ray diffraction. The resulting carboxonium derivatives are capable of protonation to form neutral systems of the general form [2,6-B<sub>10</sub>H<sub>8</sub>O<sub>2</sub>CC<sub>6</sub>H<sub>4</sub>R(H<sup>fac</sup>)]<sup>0</sup>, where R = F, CH<sub>3</sub>, C<sub>3</sub>H<sub>7</sub>, C<sub>6</sub>H<sub>5</sub>. When a protonated carboxonium derivative of acetonitrile is added to a solution, a trisubstituted derivative of the general form [B<sub>10</sub>H<sub>7</sub>O<sub>2</sub>CC<sub>6</sub>H<sub>4</sub>R(NCCH<sub>3</sub>)]<sup>0</sup> is formed.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"68 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142251739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-15DOI: 10.1134/s0036023624601892
M. N. Ryabchikova, A. V. Nelyubin, I. N. Klyukin, N. Yu. Karpechenko, A. P. Zhdanov, K. Yu. Zhizhin, N. T. Kuznetsov
Abstract
A series of amidine derivatives of the closo-decaborate and closo-dodecaborate anions with triethylammonium cations were obtained. The structures of the compounds was determined by multinuclear NMR spectroscopy and ESI-mass spectrometry. Cytotoxicity of all compounds obtained was investigated by MTT method on four cell lines. It was shown that the nature of the cation does not affect the cytotoxicity of the substituted closo-borates discussed.
摘要 获得了一系列以三乙基铵为阳离子的癸羧酸盐和十二羧酸盐脒衍生物。这些化合物的结构是通过多核核磁共振波谱和 ESI 质谱法确定的。用 MTT 法研究了所有化合物对四种细胞系的细胞毒性。结果表明，阳离子的性质并不影响所讨论的取代封闭硼酸盐的细胞毒性。
{"title":"Synthesis of Triethylammonium Salts of Amidine Derivatives of closo-Borate Anions [B10H10]2– and [B12H12]2– and Study of Their Cytotoxic Properties","authors":"M. N. Ryabchikova, A. V. Nelyubin, I. N. Klyukin, N. Yu. Karpechenko, A. P. Zhdanov, K. Yu. Zhizhin, N. T. Kuznetsov","doi":"10.1134/s0036023624601892","DOIUrl":"https://doi.org/10.1134/s0036023624601892","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>A series of amidine derivatives of the <i>closo</i>-decaborate and <i>closo</i>-dodecaborate anions with triethylammonium cations were obtained. The structures of the compounds was determined by multinuclear NMR spectroscopy and ESI-mass spectrometry. Cytotoxicity of all compounds obtained was investigated by MTT method on four cell lines. It was shown that the nature of the cation does not affect the cytotoxicity of the substituted <i>closo</i>-borates discussed.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"4 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142251743","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-15DOI: 10.1134/s0036023624602046
P. G. Gagarin, A. V. Guskov, V. N. Guskov, A. V. Khoroshilov, K. S. Gavrichev
Abstract
The temperature stages of crystallization process for thulium titanate of pyrochlore structural type during the heating of hydroxide precursor obtained by reverse precipitation have been studied by DSC/TG, XRD, and electron microscopy. Tm2Ti2O7 has been measured in the temperature range 2–1870 K and thermodynamic functions at 0–1900 K and the Gibbs energy of formation from oxides and elements have been calculated based on smoothed heat capacity. The contribution of the Schottky anomaly at 20–320 K into heat capacity has been revealed.
摘要 利用 DSC/TG、XRD 和电子显微镜研究了通过反向沉淀获得的氢氧化物前驱体在加热过程中热绿球石结构类型的钛酸铥结晶过程的温度阶段。在 2-1870 K 的温度范围内测量了 Tm2Ti2O7，并根据平滑热容计算了 0-1900 K 的热力学函数以及氧化物和元素形成的吉布斯能。揭示了 20-320 K 时肖特基异常对热容量的贡献。
{"title":"Synthesis and Thermodynamic Properties of Thulium Titanate","authors":"P. G. Gagarin, A. V. Guskov, V. N. Guskov, A. V. Khoroshilov, K. S. Gavrichev","doi":"10.1134/s0036023624602046","DOIUrl":"https://doi.org/10.1134/s0036023624602046","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>The temperature stages of crystallization process for thulium titanate of pyrochlore structural type during the heating of hydroxide precursor obtained by reverse precipitation have been studied by DSC/TG, XRD, and electron microscopy. Tm<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub> has been measured in the temperature range 2–1870 K and thermodynamic functions at 0–1900 K and the Gibbs energy of formation from oxides and elements have been calculated based on smoothed heat capacity. The contribution of the Schottky anomaly at 20–320 K into heat capacity has been revealed.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"39 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142251738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-15DOI: 10.1134/s0036023624601788
K. F. Shumovskaya, M. E. Komshina, M. V. Sukhanov, S. D. Plekhovich, A. D. Plekhovich, P. A. Otopkova, O. Yu. Troshin, A. D. Bulanov
Abstract
Samples of amorphous silicon dioxide have been synthesized from silicon with natural isotope abundance; silicon highly enriched in silicon-28, silicon-29, or silicon-30 with a degree of enrichment from 99.29 ± 0.01 to 99.9980 ± 0.0010 at %; and silicon being a mixture of silicon-28 and silicon-30. The samples were studied by IR spectroscopy. The IR spectra of the samples demonstrate a low-frequency shift of the known stretching and bending vibration absorption bands for the silicon-29 and silicon-30 isotopes by 0.1–30.1 cm–1 compared to silicon-28. For the silicon dioxides containing a mixture of silicon-28 and silicon-30 isotopes and with natural isotope composition, there is a deviation from the linear dependence of the vibration frequency of monoisotopic samples. The positions of the absorption band maxima in the model IR spectrum of silicon dioxide have been calculated by the DFT method. The results obtained correlate with experimental data with high accuracy. The reduced mass and force constant of vibrating groups of atoms in silicon dioxide were determined, and the influence of these factors on the isotopic shift in the IR spectrum of silicon dioxide, depending on the type of vibration, was established.
{"title":"Isotope Effect in IR Spectra of Highly Enriched Amorphous Silicon Dioxide ASiO2 (A = 28, 29, 30)","authors":"K. F. Shumovskaya, M. E. Komshina, M. V. Sukhanov, S. D. Plekhovich, A. D. Plekhovich, P. A. Otopkova, O. Yu. Troshin, A. D. Bulanov","doi":"10.1134/s0036023624601788","DOIUrl":"https://doi.org/10.1134/s0036023624601788","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Samples of amorphous silicon dioxide have been synthesized from silicon with natural isotope abundance; silicon highly enriched in silicon-28, silicon-29, or silicon-30 with a degree of enrichment from 99.29 ± 0.01 to 99.9980 ± 0.0010 at %; and silicon being a mixture of silicon-28 and silicon-30. The samples were studied by IR spectroscopy. The IR spectra of the samples demonstrate a low-frequency shift of the known stretching and bending vibration absorption bands for the silicon-29 and silicon-30 isotopes by 0.1–30.1 cm<sup>–1</sup> compared to silicon-28. For the silicon dioxides containing a mixture of silicon-28 and silicon-30 isotopes and with natural isotope composition, there is a deviation from the linear dependence of the vibration frequency of monoisotopic samples. The positions of the absorption band maxima in the model IR spectrum of silicon dioxide have been calculated by the DFT method. The results obtained correlate with experimental data with high accuracy. The reduced mass and force constant of vibrating groups of atoms in silicon dioxide were determined, and the influence of these factors on the isotopic shift in the IR spectrum of silicon dioxide, depending on the type of vibration, was established.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"23 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142251740","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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