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2017 year, number 5
Yu. Yu. Bozhko, O. S. Subbotin, K. V. Gets, R. K. Zhdanov, V. R. Belosludov
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: решеточная динамика, термодинамические свойства, фазовые равновесия, двойные клатратные гидраты, закись азота, ксенон, lattice dynamics, thermodynamic properties, phase equilibria, double clathrate hydrates, nitrous oxide, xenon
Abstract >>
Structural, dynamic, and thermodynamic features of double hydrates of xenon and nitrous oxide are calculated. Thermodynamic stability regions of these hydrates are found. At the atmospheric pressure the xenon hydrate is in the equilibrium with the gas phase at temperatures up to 263 K, whereas at these pressures the nitrous oxide hydrate decomposes already at 218 K. A strong dependence of the equilibrium temperatures and pressures of the formation/decomposition of double nitrous oxide and xenon hydrates on the composition of their mixture in the gas phase is shown.
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M. R. Ryzhikov1,2, S. G. Kozlova1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: кластерные трехъядерные соединения железа, индуцируемые токи, химические сдвиги ЯМР Н, теория функционала плотности, trinuclear iron cluster compounds, induced currents, Н NMR chemical shifts
, density functional theory
Abstract >>
The quantum chemical calculations of induced electric currents in (μ-H)2Fe3(μ3-Q)(CO)9 complexes, where Q = S, Se, Te, are carried out. It is demonstrated that the appearance of anomalous 1Н NMR chemical shifts on bridging hydrogen atoms is, first of all, due to the effect of induced currents on iron atoms.
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L. N. Mazalov1,2, S. A. Lavrukhina1, A. D. Fedorenko1, G. I. Semushkina1, A. V. Kalinkin3
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia 3Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: рентгеновская эмиссионная спектроскопия, рентгеновская фотоэлектронная спектроскопия, квантово-химические расчеты, метод DFT, каликс[4]аренфосфиноксиды, тиакаликс[4]аренфосфиноксиды, экстрагент, X-ray emission spectroscopy, X-ray photoelectron spectroscopy, quantum chemical calculations, DFT method, calix[4]arene phosphine oxides, thiacalix[4]arene phosphine oxides, extractant
Abstract >>
The electronic structure of calix[4]arene phosphine oxides (CPO) and thiacalix[4]arene phosphine oxides (TCPO) is studied by X-ray photoelectron and emission spectroscopy and quantum chemical methods. The electron density distribution over atoms contained in CPO and ТCPO is analyzed. The structure of higher occupied molecular orbitals (HOMO) is examined. It is shown that HOMOs of these compounds mainly consist of contributions of oxygen 2 p atomic orbitals (AOs) of phosphoryl and hydroxyl moieties and also bridging sulfur 3 p АОs, which indicates the bifunctionality of the considered extractant molecules. The mutual effect of the lower and upper rims of CPOs and ТCPOs as well as the effect of their structures on the electron density distribution over calixarene molecules is investigated
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Yu. V. Fedoseeva1,2, T. A. Duda3, A. G. Kurenya1, A. V. Gusel'nikov1, K. S. Zhuravlev3, O. Yu. Vilkov4, L. G. Bulusheva1,2, A. V. Okotrub1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National State Research University, Novosibirsk, Russia 3Rzhanov Institute of Semiconductor Physics, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 4St. Petersburg State University, Sankt-Peterburg, Russia
Keywords: наночастицы CdS, углеродные нанотрубки, рентгеновская фотоэлектронная спектроскопия, рентгеновская спектроскопия поглощения, электронное строение, CdS nanoparticles, carbon nanotubes, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, electronic structure
Abstract >>
The composition and electronic structure of cadmium sulfide (CdS) nanoparticles formed by the Langmuir-Blodgett (LB) technique on clean silicon wafers and the surface of vertically aligned carbon nanotube (CNT) arrays are studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The samples were annealed in a vacuum at 175 °C and 225 °C to remove the organic matrix of the LB film. From the analysis of the XPS data the increased concentration of sulfate groups on the surface of CdS nanoparticles formed on CNTs and the electron density transfer from CdS to CNTs are determined. An increase in the LB film annealing temperature causes an increase in the degree of crystallinity and the CdS crystallite size and a decrease in the photoluminescence intensity of a CdS-CNT hybrid.
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A. A. Ryadun, V. A. Nadolinny, O. V. Antonova, M. I. Rakhmanova
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: люминесценция, ЭПР спектроскопия, кристаллы трибората лития, катионные вакансии, luminescence, EPR spectroscopy, lithium triborate crystals, cation vacancies
Abstract >>
An attempt is made to explain the causes of coloration of LiB3O5 crystals after their long-term operation as laser elements. By EPR and optical spectroscopy the impurity and radiation centers are studied in as-grown LiB3O5 crystals and in the crystals whose color appeared after the long-term operation as laser elements. In a number of as-grown crystals a copper impurity is detected. EPR spectral parameters and the structural positions of Cu2+ ions are found. Defect formation features in electron irradiated as-grown LiB3O5 crystals and in the most colored regions of crystals of spent laser elements are analyzed. It is shown that in both growth crystals and crystals after long-term operation as laser elements the same set of radiation defects is observed: oxygen О- in the interstitial position, an О- hole center in the crystal structure, and the В2+ electron center due to the removal of an oxygen atom near the lithium vacancy. The only distinction is that the concentration of these radiation defects in crystals long used as laser elements is higher than that in growth ones by an order of magnitude. The results obtained enable the conclusion that the cause of coloration of LiB3O5 crystals is photo-induced diffusion of lithium atoms and their capture by cation vacancies in the dark part of the crystal, which provides the formation and accumulation of lithium vacancies in the region where the laser beam passes.
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A. I. Romanenko1,2, G. E. Yakovleva1, V. E. Fedorov1,3, A. Yu. Ledneva1, V. A. Kuznetsov1, A. V. Sotnikov1, A. R. Tsygankova1,3, B. M. Kuchumov1
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Tomsk National Research State University, Tomsk, Russia 3Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: слоистые халькогениды переходных металлов, электропроводность, термоэдс, layered transition metal chalcogenides, electrical conductivity, Seebeck coefficient
Abstract >>
Temperature dependences of the electrical conductivity are studied in the range 4.2-300 K and Seebeck coefficient at room temperature of bulk samples of tungsten dichalcogenide polycrystals with niobium substitutions for tungsten and selenium substitutions for sulfur - W1- x Nb x (S1- y Se y )2. The two-dimensionalization of electron transport properties is detected at niobium concentrations x ³ 0.1 in W1- x Nb x S2 and x ³ 0.05 in W1- x Nb x Se2. In samples with additional partial selenium substitution for sulfur the electron transport remains three-dimensional. At room temperature the Seebeck coefficient (at equal electrical conductivities) is several times higher in the samples with quasi-two- dimensional transport than in the samples with three-dimensional transport. The calculation of the power factor at room temperature shows its nine times increase.
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T. I. Asanova1, I. P. Asanov1,2, M.-G. Kim3, S. V. Korenev1,2
1Nikolaev Institute of Inorganic Chemistry Siberian Branch, Russian Academy of Science, Novosibirsk ,Russia 2Novosibirsk National Research University, Novosibirsk ,Russia 3Pohang University of Science and Technology, Pohang, Republic of Korea
Keywords: наносплав PtOs, биметаллические наночастицы, [Pt(NH)][OsCl], механизм термического разложения, XAFS, РФЭС, размерный эффект, PtOs nanoalloy, bimetallic nanoparticles, mechanism of thermal decomposition, XPS, size effect
Abstract >>
In the paper results of the investigation of the thermal decomposition process of double complex salt [Pt(NH3)4][OsCl6] by x-ray absorption (XAFS) and photoelectron (XPS) spectroscopies have been presented. The data obtained allows a mechanism of the thermal decomposition to be refined. An influence of size effect and nanoalloy formation on chemical shift of Pt and Os is discussed.
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Yu. A. Galkina1,2, N. A. Kryuchkova1, M. A. Vershinin1, B. A. Kolesov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: спектры КР, сильные водородные связи, квантово-химический расчет, изотопозамещение, Raman spectra, strong hydrogen bonds, quantum chemical calculation, isotopic substitution
Abstract >>
The work deals with the establishment of the dependence of the vibrational frequencies of strong O-H…O and N-H…O hydrogen bonds for the diagnosing the bonds themselves. To this end, the Raman spectra of a large number of different normal and deutero-substituted crystals characterized by the presence of strong O-H…O and N-H…O bonds are measured and the quantum chemical calculation is performed for one of these compounds. The dependence of the O-H stretching frequency on the O…O distance is constructed differing from that previously known for short O…O contacts. The mechanisms of significant broadening of the O-H vibration band in strong O-H…O hydrogen bonds are considered. Different dependences of the N-H vibrational frequencies in N-H…O bonds are reported and the causes of this diversity are discussed.
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O. G. Shakirova1, L. G. Lavrenova2,3, N. V. Kuratieva2,3, A. S. Bogomyakov3,4, L. A. Sheludyakova2,3, A. P. Mosalkova5, Yu. V. Grigoriev5
1Komsomolsk-on-Amur State Technical University, Komsomolsk-on-Amur, Russia 2Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 3Novosibirsk National Research State University, Novosibirsk, Russia 4International Tomography Center, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 5Belarusian State University, Minsk, Belarus
Keywords: синтез, координационные соединения, железо(II), 2-(2-трет-бутилтетразол-5-ил)пиридин, структура, магнитные свойства, synthesis, coordination compounds, iron(II), 2-(2-tert-butyltetrazol-5-yl)pyridine, structure, magnetic properties
Abstract >>
Iron(II) dicyanamide and isothiocyanate compounds with 2-(2- tert -butyltetrazol-5-yl)pyridine (L) of the composition [FeL2(C2N3)2]×2H2O (I) and [FeL2(NCS)2]H2O (II) are synthesized and studied. The compounds are examined using powder and single crystal XRD (for I), electron (diffuse reflectance spectra) and IR spectroscopy, static magnetic susceptibility. The analysis of the dependence meff( Т ) indicates that the exchange interactions of antiferromagnetic nature appear between the iron(II) ions at temperatures below 50 K.
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S. P. Gabuda†1, S. G. Kozlova1,2, N. B. Kompankov1, K. S. Redkina2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: водный раствор триэтиламина, фазовый переход, ЯМР Н, aqueous triethylamine solution, phase transition, Н NMR
Abstract >>
The 1Н NMR spectra in a binary aqueous triethylamine solution are recorded with a lower critical point of the liquid-liquid phase transition. It is found that, above the critical temperature the 1Н NMR spectra of water and triethylamine molecules in the phase with a predominant content of triethylamine molecules are characterized by an inhomogeneous broadening. It can be supposed that the found broadening is due to the features of the molecular distribution at the interface.
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N. V. Podberezskaya1, V. Yu. Komarov1,2, M. Yu. Kameneva1, L. P. Kozeeva1, A. N. Lavrov1
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: кобальтаты, монокристаллы, нестехиометрия по кислороду, структурный анализ, обработка рентгендифракционных данных, структурные модели, cobaltates, single crystals, oxygen non-stoichiometry, structural analysis, X-ray diffraction data processing, structural models
Abstract >>
Impurity-free R BaCo4O7+ x ( R = Y, Lu) crystals are grown and the evolution of their structure with varying oxygen concentration in the range 0 £ x £ 1.3 is studied. The structural features of the studied samples required to develop an extended strategy of the X-ray crystallographic experiment, which made it possible to obtain more accurate data on unit cell parameters and additional information on the features of superstructure modulation and diffuse scattering, along with the phase composition of crystalline samples. A crystal chemical analysis of the known structural models of R BaCo4O7+ x is performed and suggestions are made about possible structural changes occurring when the oxygen concentration increases up to the limit.
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S. V. Borisov, N. V. Pervukhina, S. A. Magarill
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: кристаллографический анализ, катионные подрешетки, механико-волновая концепция кристаллического состояния, когерентная сборка, механизм кристаллизации, crystallographic analysis, cation sublattices, mechanical-wave concept of crystal state, coherent assembly, crystallization mechanism
Abstract >>
By means of the mechanical-wave concept of crystal state and the crystallographic analysis the universal regularities of the crystal structure formation are determined: presudotranslational ordering of atoms within unit cells; separate ordering of different groups of atoms with the alignment of their sublattice parameters; the principle of coherent assembly a structure from stable building blocks with the local geometry and block symmetry spread on the structure formed, and so on. The crystallization mechanism is illustrated by specific structures.
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V. V. Bakakin
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: катионные каркасы, темплаты, ортобораты, фторидобораты бария, фторидобораты свинца, антицеолиты, cation frameworks, templates, orthoborates, barium fluoride borates, lead fluoride borates, antizeolites
Abstract >>
The crystallogenesis of three groups of structures of fluoride-orthoborates (and their analogs) with large cations is studied from the point of view of the current cation-framework representations. Their cation frameworks are sterically templated by rigid borate anions and are built as antizeolite structures. Cavities of channel or layered types are filled with components different their composition and configuration with the main function as charge compensators. An example of different functionalities of the identical anions are Ba3(BO3)2 and La3Ca3(BO3)5 structures. In these structures, two (BO3) types generate a cation framework, and the third type stabilizes it in ready channels (!).
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A. S. Sukhikh1,2, T. V. Basova1,2, S. A. Gromilov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University
Keywords: рентгеновская дифрактометрия поликристаллов, ориентированные образцы, тонкие пленки, индицирование, фталоцианины палладия, X-ray diffractometry of polycrystals, oriented samples, thin films, indexing, palladium phthalocyanines
Abstract >>
An approach for the substantiated choice of the indexing procedure of a diffraction pattern is described. The technique is based on a combined use of powder X-ray diffraction data in Bragg-Brentano schemes and 2D GIXD of mainly oriented polycrystalline samples.
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Ya. S. Fomenko1, A. L. Gushchin1,2, V. A. Nadolinny1, P. A. Abramov1, M. N. Sokolov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: ванадий, дитиолатные комплексы, кристаллическая структура, спектры ЭПР, vanadium, dithiolate complexes, crystal structure, EPR spectra
Abstract >>
The tris-chelate complex of vanadium(IV) (Bu4N)2[V(dmit)3] is prepared from VCl3 and (Bu4N)2[Zn(dmit)2] (dmit = isotrithionedithiolate C3S52-) and characterized by single crystal XRD and mass spectrometry. The complex crystallizes in the space group Pna 21 and has a distorted octahedral environment of vanadium. The complex is paramagnetic and gives a characteristic EPR spectrum in both solution and solid phase. The g factors and hyperfine interaction constants are determined.
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G. I. Zharkova, I. A. Baidina, A. I. Smolentsev, P. A. Stabnikov, N. B. Morozova
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: ОІ-иминокетонаты Pt(II), структура, летучесть, прекурсор для MOCVD, Pt(II)ОІ-iminoketonates, structure, volatility, MOCVD precursor
Abstract >>
A novel volatile Pt(II)b-iminoketonate complex is synthesized. b-Aminovinylketone H(i-ptac) = [CF3-C(O)-CH=C(NH2)-C(CH3)3] is used as a ligand. The XRD method is used to determine the structures of the ligand and the complex. The crystallographic data for C16H22F6N2O2Pt are as follows: a = 10.0716(4) Å, b = 10.9572(4) Å, c = 9.6322(4) Å, b = 110.9010(10)°, space group С 2/ m , Z = 2, R = 0.011. The platinum atom has a square planar coordination with two oxygen and two nitrogen atoms of two bidentately linked ketoiminate ligands in trans -position; the PtO2N2 coordination site is formed.
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V. A. Vorobyev1,2, V. A. Emelyanov1,2, I. A. Baidina1, D. A. Piryazev1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: рутений, нитрозокомплексы, нитратокомплексы, амминокомплексы, отработанное ядерное топливо, рентгеноструктурный анализ, расчеты DFT, ruthenium, nitrosyl complexes, nitrato complexes, ammine complexes, spent nuclear fuel, single crystal X-ray diffraction analysis, DFT calculations
Abstract >>
Single crystal X-ray diffraction is used to study the nitrosoruthenium mer- trinitrato complex [RuNO(NH3)2(NO3)3]. The crystallographic data for H6N6O10Ru are as follows: a = 7.6477(1) Å, b = 10.8404(2) Å, c = 24.0168(6) Å, a = b = g = 90°, V = 1991.09(7) Å3, Z = 8, d calc = 2/338 g/cm3, space group Р 212121. The structure is formed of two structurally non-equivalent uncharged mer- [RuNO(NH3)2(NO3)3] complexes. The complex crystallizes as yellow needles or orange powder belonging to the orthorhombic system. The substance is poorly soluble in water, ethanol, and acetone, stable in dark storage. The comparisons with the EXAFS data for this complex and the theoretical DFT calculations with different functionals are performed.
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D. V. Bonegardt1,2, I. Yu. Il'in1, T. S. Sukhikh1,2, N. B. Morozova1
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: иридий(I), 1,5-циклооктадиен, пентаметилциклопентадиен, рентгеноструктурный анализ, термогравиметрия, iridium(I), 1,5-cyclooctadiene, pentamethylcyclopentadiene, single crystal X-ray diffraction analysis, thermogravimetry
Abstract >>
Volatile iridium(I) complexes [Ir(cod)Cpx] (Cpx = pentamethylcyclopentadienyl Cp*, ethylcyclopentadienyl CpEt, cod = 1,5-cyclooctadiene) are synthesized and characterized by IR and NMR spectroscopy. The [Ir(cod)Cp*] complex is a solid and the [Ir(cod)CpEt] complex is a liquid (SATP). The XRD method is used to determine the structure of the [Ir(cod)Cp*] complex: chemical formula C18H27Ir, space group P21/ с , a = 8,4418(2) Å, b = 9,4764(3) Å, c = 19.2682(5) Å, β = 96.128(1) °, V = 1532.61(7) Å3, Z = 4, d calc = 1.888 g/cm3, m = 8.697 mm-1. The cyclopentadienyl ligand is h5-type coordinated; 1,5-cyclooctadiene have a cis - cis conformation and is h4-type coordinated. The thermal properties of the complexes are studied by thermogravimetry.
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A. A. Ivanov1, N. V. Kuratieva1,2, M. A. Shestopalov1,2, Yu. V. Mironov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: рений, кристаллическая структура, октаэдрические халькогенидные кластеры, rhenium, crystal structure, octahedral chalcogenide clusters
Abstract >>
A cluster complex of the composition [CsK2(m3-DMF)2(m-DMF)3(DMF)4][{Re6(m3-Se)8}Br6] is obtained by the reaction of K4[{Re6(m3-Se)8}(OH)6]×8H2O with hydrobromic acid in the presence of CsBr and its subsequent crystallization by diethyl ether diffusion in a dimethylformamide solution. The compound crystallizes in the triclinic space group P , with the following unit cell parameters: a = 13.6169(3) Å, b = 14.7584(4) Å, c = 18.1573(4) Å, a = 103.332(1)°, b = 108.250(1)°, g = 97.371(1)°, V = 3286.55(14) Å3, Z = 2, d calc = 3.130 g/cm3. The crystal structure is built of [{Re6Se8}Br6]3- anionic cluster complexes and complex [CsK2(m3-DMF)2(m-DMF)3(DMF)4]3+ cations.
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T. E. Kokina1,2, L. A. Glinskaya1, E. S. Vasiliev3, M. I. Rakhmanova1, S. V. Makarova2, D. A. Piryazev1,2, I. V. Korol'kov1,2, A. V. Tkachev2,3, S. V. Larionov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia 3Vorozhtsov Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: терпены, бис-пиридин, комплексы Zn(II) и Cd(II), структура, фотолюминесценция, terpenes, bis-pyridine, Zn(II) and Cd(II) complexes, structure, photoluminescence
Abstract >>
Complexes ZnLCl2 (I) and [CdLCl2] n (IV), where L is chiral bis -pyridine containing fragments of natural monoterpenoide (-)-a-pinene are synthesized. Single crystals of [ZnLCl2]×CH2Cl2 (II), [ZnLCl2]× i -PrOH (III), and IV compounds are grown. The crystal structures of II and III are composed of mononuclear ZnLCl2 complex molecules and solvate CH2Cl2 and i -PrOH molecules; the coordination polyhedron of the zinc atom Cl2N2 is a distorted tetrahedron. According to the single crystal XRD data, complex IV is a 1D coordination polymer; the coordination core CdN2Cl4 is a distorted octahedron and Cl atoms are bridging ligands. In the structures of II, III, and IV the L molecule functions as a bidentate chelate ligand. In the solid phase, complexes I and IV exhibit photoluminescence in the visible range (lmax 505 nm and 460 nm respectively). The band intensity in the photoluminescence spectra of I and IV complexes considerably exceeds the band intensity in the spectrum of free L.
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N. V. Kuratieva1,2, E. S. Vikulova1, A. D. Shushanyan1,2, N. S. Nikolaeva1, S. I. Dorovskikh1,2, N. S. Mikhaleva1, N. B. Morozova1
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: палладий(II), медь(II), ОІ-кетоиминат, рентгеноструктурный анализ, palladium(II), copper(II), ОІ-iminoketone, single crystal X-ray diffraction
Abstract >>
Palladium(II) and copper(II) complexes with 2-(2,2-dimethylhydrazone) pentanone-4 are synthesized for the first time. The compounds are characterized by IR and NMR spectroscopy, elemental and single crystal X-ray diffraction analyses. The palladium complex crystallizes in the space group I 41/ a ; the copper complex crystallizes in the space group P . Both compounds are molecular; the palladium chelate core has a distorted square geometry and that of copper has a distorted tetrahedral geometry. The average M-O and M-N bond lengths are respectively 1.9808(15) Å and 2.0427(17) Å for M = Pd, 1.915(8) Å and 1.97(1) Å for M = Cu. The chelate O-M-N angles are 88.32(7)-91.67(7)° for M = Pd, 93.37(4)-99.02(5)° for M = Cu.
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I. G. Vasilyeva
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: четверной сульфид медь-хром-ванадия, химическая неоднородность, разупорядочение, фазовые переходы, quaternary copper-chromium-vanadium sulfide, chemical heterogeneity, disordering, phase transitions
Abstract >>
A gradient chemical structure of micron-sized crystals of CuCrS2 and CuCr1- x V x S2 powders is established by the differential dissolution technique. It is shown that their surface region coherently conjugated with planar faces of CuCrS2 crystals is enriched with copper whereas the bulk is depleted of copper and the copper sublattice is disordered. A possible mechanism of the formation of surface regions due to a high bulk mobility of copper atoms in the defect copper sublattice is proposed. It is shown that for solid solutions the disordering process involves copper and vanadium atoms and vacancy complexes. The phenomena found are discussed together with the structural and magnetic data.
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I. S. Merenkov1, I. A. Kasatkin2, E. A. Maksimovskii1, N. I. Alferova1, M. L. Kosinova1
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2St. Petersburg State University, St. Petersburg, Russia
Keywords: гексагональный нитрид бора, наностенки, PECVD, триэтиламинборан, hexagonal boron nitrides, nanowalls, PECVD, triethylaminoborane
Abstract >>
A low-temperature plasma enhanced chemical vapor deposition procedure is developed for hexagonalого boron nitride nanowalls that are an array of sheets vertically aligned relative to the Si(100) substrate. A triethylaminoborane and ammonia gas phase was used for the first time to form h-BN nanowalls. Nanowall sizes are 50-250 nm long and 10-25 nm thick. Grazing incidence X-ray diffraction and high-resolution transmission electron microscopy techniques are employed to study the structures of boron nitrideх nanowalls. The effect of synthesis parameters (film deposition temperature and growth time) on the chemical and phase compositions, surface morphology, film structure, and their optical properties are analyzed.
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T. Yu. Podlipskaya, A. I. Bulavchenko
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: смешанные обратные мицеллы, Triton N-42, AOT, экстракция, гидратная (связанная) вода, объемная (свободная) вода, ИК-Фурье спектроскопия, mixed reverse micelles, Triton N-42, AOT, extraction, hydration (bound) water, bulk (free) water, FTIR spectroscopy
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FTIR spectroscopy is used to study the distribution of bulk (free) and hydration (bound) water during the extraction of Au(III) and Pt(IV) from acid sulfate-chloride media by reverse micelles consisting of non-ionic (Triton N-42) and anionic (AOT) surfactants. It is shown that the bulk water fraction increases with an increase in the anionic AOT concentration and that of hydration water increases with an increase in the non-ionic Triton N-42 concentration. A decrease in the bulk water fraction and an increase in the hydration water content enhance the extraction capacity of mixed micelles.
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P. A. Poltarak1,2, A. A. Poltarak1,2, S. B. Artemkina1,2, T. Yu. Podlipskaya1,2, V. E. Fedorov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: слоистые соединения, трисульфид титана, коллоидная дисперсия, ультразвуковое диспергирование, наночастицы трисульфида титана, фотон-корреляционная спектроскопия, гидродинамический диаметр, просвечивающая электронная микроскопия, layered compounds, titanium trisulfide, colloidal dispersion, ultrasonic dispersing, titanium trisulfide nanoparticles, photon correlation spectroscopy, hydrodynamic diameter, transmission electron microscopy
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Stable colloidal dispersions with a 2 mM TiS3 concentration (300 mg/l) are obtained by ultrasonic treatment of TiS3 in acetonitrile and isopropyl alcohol and characterized by physicochemical methods. The electrical double layers for the particles in dispersions are estimated from the measured z-potentials, and the energies of interparticle interactions are calculated based on the Derjaguin-Landau-Verwey-Overbeek theory. The structural and spectroscopic identity of the particles and crystalline TiS3 is demonstrated for the solid phases obtained from the dispersions.
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A. S. Sukhikh, M. S. Polyakov, D. D. Klyamer, S. A. Gromilov, T. V. Basova
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: фталоцианины металлов, молекулярные пленки, РФА, химические сенсоры, metal phthalocyanine, molecular films, powder XRD, chemical sensors
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A comparative study of the structural features of zinc 2,9,16,23-tetra- tert -butylphthalocyanine films (ZnPc( t Bu)4) obtained by vacuum thermal deposition and spin coating techniques is performed. By powder X-ray diffraction, 2D GIXD, and optical absorption spectroscopy it is shown that ZnPc( t Bu)4 films obtained by the spin coating technique consist of a disordered a-phase with small crystallites. After annealing at 200 °C for 3 h the films transform into the b-phase, with crystallite sizes increasing, however, they remain disordered relative to the substrate surface. On heating under the same conditions, the ZnPc( t Bu)4 films obtained by thermal vacuum sublimation transform from the weakly oriented low-temperature a-phase into the oriented b-phase. Dependences of a chemiresistive sensor response of the ZnPc( t Bu)4 films to ammonia (10-50 ppm) are investigated depending on the preparation and annealing methods of the films.
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T. K. Koltunova1, D. G. Samsonenko1,2, D. N. Dybtsev1,2, V. P. Fedin1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: координационные полимеры, каркасные структуры, комплексы лития(I), рентгеноструктурный анализ, coordination polymers, framework structures, lithium(I) complexes, single crystal X-ray diffraction analysis
Abstract >>
Three new metal-organic coordination polymers (H2NMe2)2[Li3(btc)(Hbtc)(DMF)4] (1), [Li5(DMF)6(btc)(Hbtc)]×2DMF (2), and [Li6(DMF)8(bdc)(Hbtc)] (3) (H3btc is trimesic acid, H2bdc is terephthalic acid) are prepared by heating LiOH with different aromatic carboxylic acids in dimethyl formamide (or its mixture with water). The crystal structures and composition of the compounds are determined by single crystal X-ray diffraction. Compound 1 has a layered structure; compounds 2 and 3 have a framework structure.
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