Разработан и оптимизирован синтез двойной комплексной соли (ДКС) [Pd(NH3)4][VO(H2O)(C2O4)2]∙2H2O. Соединение охарактеризовано методами рентгеноструктурного и рентгенофазового анализа, инфракрасной спектроскопией и спектроскопией диффузного отражения. Кристаллографические данные: пространственная группа P-1, a = 7.3160(10) Å, b = 8.2700(2) Å, c = 12.9205(2) Å, α = 71.576(10)°, β = 78.477(10)°, γ = 83.844(10)°, Z=2. Методом ЭПР установлено наличие обменного взаимодействия между комплексными анионами. Изучен процесс термического разложения ДКС в инертной и восстановительной атмосферах. Установлено, что конечным продуктом термолиза в восстановительной атмосфере является смесь твердого раствора состава Pd0.90V0.10 и оксида ванадия(III). Проведены теоретические расчёты СДО для полученной ДКС.

Разработан новый метод получения магнитных композитных пленок сложного состава SiCxNyFez плазмохимическим разложением в ВЧ плазме газовой смеси 1,1,1,3,3,3-гексаметилдисилазана [(CH3)3Si]2NH, ферроцена (C5H5)2Fe и гелия He. Пленки различного состава получены в интервале температур осаждения 373—873 K. Установлена зависимость физико-химических и функциональных свойств пленок SiCxNyFez от условий синтеза с помощью комплекса современных методов исследования, таких как: ИК спектроскопия, КРС спектроскопия, ЭДС, РФЭС, рентгенофазовый анализ. Обнаружено, что ИК спектры содержат тот же набор связей, что и пленки карбонитрида кремния, а в спектрах КРС наблюдаются D и G моды, свидетельствующие о присутствии примеси разупорядоченного графита. Методами Фарадея и электронного парамагнитного резонанса (ЭПР) установлено, что выращенные при температурах синтеза 573—873 K пленки SiCxNyFez являются магнитными. По данным РФЭС в пленках SiCxNyFez могут присутствовать фазы α-Fe, FeSi или β-FeSi2, близость их энергий связей затрудняет определение состава пленок.

New molecular niobium(IV) complexes NbCl4(OPPh3)2(1) and NbBr4(OPPh3)2(2) are synthesized by heating respective niobium pentahalide with a mixture of triphenylphosphine and triphenylphosphine oxide. For the obtained compounds the crystal structure is solved: 1P-1, a = 13.3540(5) Å, b = 9.4461(3) Å, c = 9.5635(3) Å, α = 93.084(1)°, β = 121.263(1)°, γ = 115.058(1)°, Z = 1, R1 = 0.0194; 2P-1, a = 13.308(2) Å, b = 9.5934(8) Å, c = 9.5556(9) Å, α = 93.975(3),°, β = 119.391(4)°, γ = 114.740(4)°, Z = 1, R1 = 0.0184. The unpaired electron is mainly located on the niobium atom, which is supported by quantum chemical calculations and EPR spectroscopic results.

Новые молекулярные комплексы ниобия(IV) NbCl4(OPPh3)2 (1) и NbBr4(OPPh3)2 (2) получены нагреванием соответствующего пентагалогенида ниобия со смесью трифенилфосфина и трифенилфосфин оксида. Для полученных соединений решена кристаллическая структура (1: P-1, a = 13.3540(5), b = 9.4461(3), c = 9.5635(3) Å, α = 93.084(1), β = 121.263(1), γ = 115.058(1)°, Z = 1, R1 = 0.0194; 2: P-1 a = 13.308(2), b = 9.5934(8), c = 9.5556(9) Å, α = 93.975(3), β = 119.391(4), γ = 114.740(4)°, Z = 1, R1 = 0.0184). Неспаренный электрон локализован преимущественно на атоме ниобия, что подтверждается квантово-химическими расчетами и результатами ЭПР спектроскопии.

The binuclear oxidovanadium(IV) complex [VO(Dbbpy)Cl(Ca)Cl(Dbbpy)VO] ( I ) is synthesized by the reaction of [VO(Dbbpy)(H 2 O)Cl 2 ] (Dbbpy is 4,4'-di- tert -butyl-2,2'-bipyridyl) with chloranilic acid H 2 Ca in acetonitrile in the presence of Et 3 N in a yield of 79%. Complex I is reduced at Е 1/2 = –842 mV (vs. Ag/AgCl), which is shown by cyclic voltammetry for a solid sample using the paste electrode. The EPR spectra and magnetochemical measurements for complex I confirm the existence of two paramagnetic vanadium(IV) centers with the total spin S = 1 and the antiferromagnetic character of the exchange interaction between the centers.

Thermodynamic modeling of the deposition of condensed phases of complex composition has been carried out in the Si–C–N–Fe–H–(He) system in the temperature range of 500–1300 K under total pressure of 10–2–10–1 Torr in the system using initial gas mixture of tris(diethylamino)silane HSi[N(C2H5)2]3, ferrocene (C5H5)2Fe, and helium. Derived from the results of thermodynamic modeling, the method for the preparation of SiC x N y Fe z films using the high-temperature decomposition of the gas mixture of TDEAS, ferrocene, and helium at low pressure in the temperature range of 1073–1273 K has been developed. The dependence of the chemical and phase composition of the films on the conditions of synthesis has been determined using various methods of chemical analysis such as IR spectroscopy, Raman scattering, scanning electron microscopy, energy dispersion spectroscopy, X-ray phase analysis using synchrotron radiation, and X-ray photoelectron spectroscopy (XPS). The magnetic properties of the films have been studied by Faraday’s method and electron paramagnetic resonance. It has been shown that the films are paramagnetic at the temperature of synthesis of 1123 K, while at the deposition temperature of 1273 K they are ferromagnetic. The mechanical properties of the films were characterized by nanoindentation technique.

By electron paramagnetic resonance spectroscopy the paramagnetic centers are investigated in SiC (x) N (y) H (z) films obtained by plasma-enhanced chemical deposition from hexamethyldisilazane vapor. It is found that the films contain dangling bonds broken at carbon atoms, their concentration considerably increasing with an increase in the deposition temperature. By Raman spectroscopy a deposition temperature range is determined within which the films contain carbon clusters. Similarity in the properties of the films synthesized at high deposition temperatures and the films initially deposited at low temperatures and then annealed is established. The results of the study are interpreted with the use of the known data on the film composition and structure and also the representations described in the literature.

Reactions of three pyrylocyanine dyes (derived from 2,4,6-trimethylpyrylium perchlorate) with p-toluidine and 2,4-diaminotoluene were studied to develop methods for detection of aromatic amines. The emission spectrum characteristics of the starting dyes and the final products obtained in solution and on silica gel were examined. The presence of open forms of the pyridocyanine dye in acetonitrile was suggested after analyzing the excitation and emission spectra of reaction intermediates. The formation of luminescent pyridocyanine in solution took several days, while its synthesis from the starting dye adsorbed on silica gel was completed within a few seconds.

Stable heterogeneous synthesis products in combined synthesis-transport processes for the growth of thin copper films have been studied by ESR, X-ray photoelectron, and IR spectroscopies. The results demonstrate that the synthesized volatile compounds condensed on solid surfaces have the form of formate-like metal complexes of copper(I). We have identified the mechanisms underlying the formation of volatile monomeric metal complexes on the surface of copper-containing precursor particles and the mechanism of the thermal decomposition of metal complexes on a heated substrate.

The origin of the magnetic field effect on the dimerization of aluminum(III) and gallium(III) phthalocyanine chloride films is revealed. The EPR technique is employed to demonstrate that the dimerization of the above coordination compounds occurs via a free radical pathway with the formation of phthalocyanine and OH radicals, thus resulting in the appearance of the magnetic moment in the studied compounds.

The transformation is studied of the compounds {[Ni(cyclam)]@CB[8]}Cl 2 ·16H 2 O and { cis -[Ni(cyclen)(H 2 O)Cl]@CB[8]}Cl·12H 2 O during thermal annealing in a temperature range of 20°C to 340°C. Using EPR spectroscopy, { cis -[Ni(cyclen)(H 2 O)Cl]@CB[8]}Cl·12H 2 O, Ni is found to reduce to the 3 d 9 state during annealing in a hydrogen atmosphere yet oxidize to the 3 d 7 state in the air at 20°C. In the case of {[Ni(cyclam)]@CB[8]}Cl 2 ·16H 2 O, nickel ions remain in the 3 d 8 state after annealing in a hydrogen atmosphere and make a transition to the 3 d 7 state after air pumping. In both cases, annealing in a hydrogen atmosphere leads to the decomposition of the nickel complexes; simultaneously, a single line with g = 2.003 appears in the EPR spectra, which is likely to be due to the resulting metal nickel clusters.

The effect is studied of electron and X-ray irradiation on phosphorous centers in synthetic diamonds grown in the P-C medium by the Bars technology. After exposure to X-ray irradiation, a new paramagnetic phosphorus-containing center NP6, in addition to the phosphorous centers NP4 and NP5, is observed in diamonds annealed at a temperature of 2300°C and pressure of 7.5 GPa. The spectrum of NP6 is simulated to give the following parameters: A 1 = 29.42 G, A 2 = 23.28 G, A 3 = 75.85 G, g 1 = 2.00085, g 2 = 2.00083, and g 3 = 2.00083. The NP4-NP6 centers are assumed to be genetically related to the three nitrogenphosphorous centers NP1-NP3 and be formed as a result of the transformation of the tetrahedral environment around the phosphorous atom into an octahedral environment at an annealing temperature of 2300°C. The synthetic diamonds annealed at 2300°C were successively exposed to irradiation with electrons with energies of 3.5 MeV (5×1017 e/cm2) and annealing at temperatures of 500°C and 700°C. The EPR method is used to find that annealing of the electron-irradiated crystals at 700°C leads to the formation of a new paramagnetic center with spin S = 1 and hyperfine structure (HFS) from one phosphorus atom with the parameters: g = 2.0012, D = 19.7 G, and A(P) = 3.6 G. The center is likely to have an eightvacancy chain structure with a phosphorus atom located at the center.

The quantization of the electronic spectrum has been observed in photoluminescence experiments for silicon quantum dots prepared by implantation of silicon into silicon dioxide SiO2. The diameter of silicon quantum dots has been estimated as 1.8 nm. Injection of electron and holes is accompanied by the appearance of a paramagnetic resonance signal with the g factor equal to 2.006. This result unambiguously indicates that silicon clusters are the electron and hole traps in SiO2.

The hydrogen reduction of bis(2,4-pentanedionato)copper(II) sorbed by the cavitand cucurbit[8]uril has been studied. After sorption of the complex at 180°C, the crystal structure of the resulting phase differs from the structure of the individual compounds. EPR shows that the reduction of the complex with hydrogen at 250°C for 15 min leads to the loss of one of the ligands and formation of the coordination bond between the Cu2+ ion and a nitrogen atom of cucurbit[8]uril and the oxygen atom of the water molecule or OH− group located in the cavitand cavity. The molecular structure of the resulting supramolecular compound has been optimized by density functional theory quantum-chemical calculations with the exchange-correlation functional with the use of the PRIRODA program package. EPR, EXAFS, and XANES show that an increase in the reduction time or temperature (to 280°C) leads to the formation of copper clusters.

This work describes EXAFS and EPR studies of inclusion compounds of the trans -[Cu(en) 2 (H 2 O) 2 ] 2+ complex in the macrocyclic cavitand CB[8] at different stages of heat treatment in the hydrogen atmosphere in a temperature range of 200–330°C. The structure and composition of the nearest environment of copper atoms are characterized, and the interatomic distances and coordination numbers are determined. It is shown that the structure of the copper complex inside the cavitand CB[8] remains unchanged at the first stage of complex preparation and upon heating up to 280°C in hydrogen atmosphere. The copper environment corresponds to four nitrogen atoms and two oxygen atoms. Further temperature treatment at 330°C causes decomposition of the complex inside the cavitand without the formation of copper clusters.

The influence of specific features of the structure and nature of the cations (Ph 4 P + , H(Phen) + , Cs + , and (CH 3 ) 4 N + ) on the ERP spectra of the nickel ions in salts with the dicarbollylnickelate anion [Ni(B 9 C 2 H 11 ) 2 ] − is studied. It is shown that the change in the cation type in these compounds results in the electron density redistribution, which affects the change in the main and average values of the g factor. The g av value increases over that observed in frozen solutions upon the localization of the positive charge of the cation on one atom and in the absence of the screening effect of the solvent and large functional groups of the cation. The exception is the compound (Ph 4 P + )NiCb 2 − (Cb is B 9 C 2 H 11 ) with solvated CCl 4 molecules. For all compounds studied, the temperature dependence of the linewidths in the EPR spectra is described by the equation ΔH = αT + βT 7 with different α and β values and is defined by the temperature dependence of the relaxation process caused by the Raman interaction.