Методом РСА изучено строение двух β-дикетонатов Al(III) и Fe(III) с γ-замещенным лигандом при 150(2) K. Кристаллографические данные для Al(γ-Me-hd)3 (I): пространственная группа P–1, a = 10.855(1) Å, b = 11.129(1) Å, с = 11.894(1) Å, α = 85.634(3)°, β = 73.118(3)°, γ = 66.771(3)°, V = 1262.2(2) Å3, Z = 2, R1 = 0.0438; для Fe(γ-Me-hd)3 (II): пространственная группа P21/с, a = 10.0374(5) Å, b = 17.0798(7) Å, с = 15.7213(6) Å, β = 107.459(1)°, V = 2571.1(2) Å3, Z = 4, R = 0.0364. Соединения I и II изотипны, так как имеют одинаковые по строению молекулы, но кристаллизуются в разных сингониях. Кристаллические структуры I и II молекулярные и состоят из дискретных молекул M(γ-Me-hd)3 (M = Al, Fe). Термогравиметрические исследования показали, что комплексы I и II обладают близкой летучестью. Для комплекса Cu(γ-Me-hd)2 (III) проведено измерение давления насыщенного пара методом Кнудсена в интервале температур 100—150 °C, установлены термодинамические параметры сублимации и исследован термолиз паров.

The structures of two Al(III) and Fe(III) β-diketonates with a γ-substituted ligand are studied by single crystal X-ray diffraction at 150(2) K. Crystallographic data for Al(γ-Me-hd)3 (I) are: space group $$P\bar{1}$$ , a = 10.855(1) Å, b = 11.129(1) Å, с = 11.894(1) Å, α = 85.634(3)°, F0200062 = 73.118(3)°, γ = 66.771(3)°, V = 1262.2(2) Å3, Z = 2, R1 = 0.0438. For Fe(γ-Me-hd)3 (II): space group P21/с, a = 10.0374(5) Å, b = 17.0798(7) Å, с = 15.7213(6) Å, F0200062 = 107.459(1)°, V = 2571.1(2) Å3, Z = 4, R1 = 0.0364. Compounds I and II are isotypical because their molecules have the same structure but crystallize in different crystal systems. The crystal structures of I and II are molecular and consist of discrete M(γ-Me-hd)3 (M = Al, Fe) molecules. Thermogravimetric studies show that complexes I and II are similarly volatile. For Cu(γ-Me-hd)2 complex (III) the saturated vapor pressure is measured by the Knudsen method in the temperature range 100-150 °C. Sublimation thermodynamic parameters are found and vapor thermolysis is investigated.

A relationship is established between the structural and thermoanalytical characteristics of the decomposition of hydrogen maleates and phthalates of Fe(II), Co(II), Ni(II), Cu(II). The temperatures of the onset of the first and second stages of decomposition grow in the series of both hydrogen maleates Cu ≤ Fe < Co < Ni and phthalates Fe ≤ Co < Ni < Cu, while the lengths of M– $${{{\text{O}}}_{{{{{\text{H}}}_{2}}{\text{O}}}}}$$ and M–Oanion bonds shrink in these structures. At the third stage, the temperature of the onset of the decarboxylation of hydrogen maleates and phthalates falls in the order Fe > Co > Ni > Cu. The size of metal nanoparticles additionally contained in a polymer or graphene shell grows from 3.5 to 5 nm (Co) and from 4.5 to 7 nm (Ni) upon moving from composites obtained through the decomposition of hydrogen maleates to hydrogen phthalates. Polymeric conglomerates containing shell-less copper nanoparticles, the average size of which ranges from 7.5 to 50 nm, are incorporated into a polymer matrix of composites obtained via the thermolysis of Cu(II) hydrogen maleate and phthalate.

The crystal structure of a hexanuclear Na(I) complex based on 3,5-dimethyl-1 H -pyrazole (C 5 H 8 N 2 ) and its anion is determined (space group P 2 1 / c , a = 12.2194(5) Å, b = 24.1554(9) Å, c = 11.3311(4) Å, β = 109.942(1)°, V = 3143.99(8) Å 3 , Z = 2). The crystal structure is formed by Na 6 (C 5 H 8 N 2 ) 4 (C 5 H 7 N 2 ) 6 molecules. Thermogravimetric studies show that the compound exhibits volatility at elevated temperatures. The compound can be used in chemical gas-phase deposition processes.

A low-temperature plasma enhanced chemical vapor deposition procedure is developed for hexagonaloro 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 nitridex 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.

A series of Ln(III) dipivaloylmethanates of the composition Ln(dpm) 3 (Ln = La, Tm, Yb) is obtained. It is established that Tm(dpm) 3 and Yb(dpm) 3 complexes are isostructural with Lu(dpm) 3 . The crystal structure of [La(dpm) 3 ] 2 at 150(2) K is determined (space group P 2 1 / n , a = 12.4412(5) Å, b = 28.0579(12) Å, с = 21.9533(8) Å, β = 105.796(2)°, V = 7373.9(5) Å 3 , Z = 4). The studied compound is isostructural with [Pr(dpm) 3 ] 2 , [Eu(dpm) 3 ] 2 , [Gd(dpm) 3 ] 2 , and [Tb(dpm) 3 ] 2 complexes. The crystal structure of the complex is formed by dimeric [La(dpm) 3 ] 2 molecules. Thermogravimetric investigations show that the volatility of Ln(dpm) 3 increases in the series from [La(dpm) 3 ] 2 to Yb(dpm) 3 . Melting points of the complexes are close to the known literature data.

Studies of the thermolysis of ortho-[Ni(H2O)2(C8H4O4)](H2O)2, [Cu(H2O)(C8H4O4)], and acid [M(H2O)6](C8H5O4)2 (M(II) = Fe(II), Co(II), and Ni(II)), [Cu(H2O)2(C8H5O4)2] phthalates reveal that the solid products of their decomposition are composites with nanoparticles embedded in carbon–polymer matrices. Metallic nanoparticles with oxide nanoparticle impurities are detected in iron/cobalt polymer composites, while nickel/copper composites are composed of only metallic particles. It is found that nickel nanoparticles with the diameters of 6–8 nm are covered with disordered graphene layers, while the copperbased composite matrix contains spherical conglomerates (50–200 nm) with numerous spherical Cu particles (5–10 nm).

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The crystal structures of the compounds with the composition [Rh(H2O)5Cl](C7H7O3S)2 (I) and Cs[Rh(H2O)5NO3](C7H7O3S)3•H2O (II) are determined. Crystallographic data for I: a = 10.063(10) Å, b = 7.771(8) Å, c = 13.524(15) Å; β = 100.44(3)°, space group P21, Z = 2, d calc = 1.823 g/cm3; for II: a = 16.221(3) Å, b = 9.646(19) Å, c = 21.307(4) Å, β = 92.06(3)°, space group P21, Z = 8, d calc = 1.833 g/cm3. The compounds are characterized by IR spectroscopy and powder X-ray diffraction. The rhodium atoms have a distorted octahedral environment consisting of five oxygen atoms of coordinated water molecules and one chloride ion (I)/oxygen atom of the nitrate ion (II) with the following distances: Rh–OH2O of 1.993-2.075 Å and Rh–Cl of 2.270 Å for I; Rh–\({O_{{H_2}O}}\) of 1.996-2.031 Å and Rh–\({O_{N{O_3}}}\) of 1.990 Å for II.

A procedure has been proposed for the preparation of copper/polymer composites through Cu(C 4 H 4 O 4 ) · H 2 O succinate thermolysis. Three types of copper nanoparticles have been incorporated into a fibrous carbon-polymer matrix of the composite: cubic (350 × 350 nm) and needle-like (40–80 nm in diameter and 4.5–5.5 μm in length) crystals and spherical copper particles (5 to 45 nm). We have compared copper succinate and copper maleate decomposition processes. The composites obtained through thermolysis have been shown to differ drastically.

A procedure for the synthesis of trans-Ru(NO)(Py)2Cl2(OH) (I) from K2[Ru(NO)Cl5] was proposed. Treatment of hydroxo complex I with HCl or H2SO4 at room temperature gave the corresponding salts trans-[Ru(NO)(Py)2Cl2(H2O)]Cl · 2H2O (II) and trans-[Ru(NO)(Py)2Cl2(H2O)]HSO4 (III). All the complexes obtained were characterized by 1H and 13C NMR and IR spectroscopy and elemental analysis; their structures were determined by X-ray diffraction. The structures are stabilized by π-stacking between the pyridine ligands of adjacent complex species.

Разработана методика синтеза композита медь/полимер термолизом сукцината Cu(C4H4O4) · H2O. В волокнистую углеродно-полимерную матрицу композита внедрены наночастицы меди трех видов: кубические (350 ? 350 нм), иглообразные (диаметром 40–80 нм, длиной 4.5–5.5 мкм) кристаллы, а также сферические частицы меди (5–45 нм). Проведено сравнение процессов разложения сукцината и малеата меди, а также образующихся в результате термолиза композитов, которое показало их кардинальное отличие.

In treatment of trans-[Ru(NO)(NH3)4(OH)]Cl2 with concentrated sulfuric acid on heating trans-[Ru(NO)(NH3)4(SO4)](HSO4)·H2O (I) is obtained with a yield close to quantitative. In the interaction of the saturated solution of I with a saturated NaNO3 solution a trans-[Ru(NO)(NH3)4(SO4)]NO3·H2O (II) precipitate forms whose structure is determined by single crystal XRD: space group P212121, a = 6.8406(3) Å, b = 12.6581(5) Å, c = 13.3291(5) Å. A monodentately coordinated sulfate ion is in the trans-position to the nitroso group. Compound II is characterized by IR spectroscopy, powder XRD, and diffuse reflectance spectroscopy. The process of its thermolysis is studied; by differential scanning calorimetry the thermal effect of the dehydration reaction occurring on heating to 120°C (ΔH = 58.9 ± 1.5 kJ/mol) is estimated. The final product of the thermolysis of II is a mixture of Ru and RuO2.

Термическим разложением нормальных [M1(H2O)2(C4H2O4)] · H2O (M1 – Co(II), Ni(II)) и кислых M2(H2O)4(С4H3O4)2 (M2 – Fe(II), Co(II), Ni(II)) малеатов синтезированы композиты металл/полимер. В полимерной матрице композита с Fe обнаружены частицы металла, а также оксидов Fe2O3 и Fe3O4, вокруг которых заметно некоторое уплотнение матрицы. В полимерную матрицу композита с Co вкраплены наноразмерные частицы 4 видов: -Co, -Co и CoO в полимерной оболочке, а также Co3O4 без полимерной оболочки. При разложении малеатов Ni образуются однородные наночастицы никеля (4–5 нм), покрытые графеновыми слоями (от 2 до 5 слоев). Композит с Co является диэлектриком. Композит с Ni при Т 50 К характеризуется прыжковой проводимостью с переменной длиной прыжка.

Metal-polymer composites have been prepared through the thermolysis of the [M 1 (H 2 O) 2 (C 4 H 2 O 4 )] · H 2 O (M 1 = Co(II), Ni(II)) neutral maleates and [M 2 (H 2 O) 4 (C 4 H 3 O 4 ) 2 ] (M 2 = Fe(II), Co(II), Ni(II)) acid maleates. In the polymer matrix of the Fe-containing composite, we identified metal, Fe 2 O 3 , and Fe 3 O 4 particles, with slight densification of the matrix around them. The polymer matrix of the cobalt maleate-derived composite contained four types of nanoparticles: α-Co, β-Co, and CoO in polymer shells and Co 3 O 4 with no polymer shell. The decomposition of the nickel maleates yielded homogeneous nickel nanoparticles (4–5 nm) covered with two to five graphene layers. The Co-containing composite was found to be a dielectric. The Ni-containing composite exhibited variable range hopping conduction in the range T ≤ 50 K.

The sol-gel method of the formation of the nanostructured luminophor based on Y 2 O 3 doped by Eu 3+ and Bi 3+ was studied. The mechanism of the dehydration and dehydroxylation of gels and xerogels of the mixed hydroxides, particle sizes, structure, and luminescent properties of the synthesized products based on Y 2 O 3 depend on the chemical nature of a precipitating agent (NaOH or NH 4 OH) and a washing agent (water and alcohol).

The thermal decomposition of neutral ([Cu(H 2 O)(C 4 H 2 O 4 )]) and acidic ([Cu(H 2 O) 4 ](C 4 H 3 O 4 ) 2 ) maleates can conventionally be divided into four stages: (1) dehydration, (2) polymerization, (3) isomerization of the maleate ion to the trans form with the simultaneous reduction Cu(II) → Cu(I), and (4) decarboxylation of copper(I) fumarate. The third and fourth stages of the decomposition of these salts coincide. The residue after the thermolysis of copper(II) maleates in a He flow is a composite consisting of aggregates from 50 nm to several microns in size. Spherical conglomerates (50–200 nm) containing many spherical Cu particles (5–10 nm) are incorporated into the organic polymer matrix of these aggregates.