Single crystals of Fe(dpm)3 (dpm - dipivaloylmethanate) are analyzed by X-ray diffraction in the temperature range of 90-365 K. A new crystal modification is found in the range of 90-100 K (space group P1̅ , Z = 8); a phase transition is confirmed to occur at 230 K (space group P1̅ , Z = 4). In the range of 250-365 K, a relative increase in the monoclinic unit cell parameters (space group C2/c, Z = 8) is Δa/a = 0.67

Crystals of copper bis(heptafluorodimethyloctanedionate) (Cu(fod)2) have been grown by evaporation of solvent from solutions. Crystals of monoclinic syngony (I) have been obtained from toluene, while crystals of monoclinic (I) and triclinic (II) syngony have been obtained from acetonitrile. Crystallographic data: P21/c, a = 13.1863 (6), b = 9.8118 (4), c = 10.6997 (6), β = 113.633(2)° for I; 1̅ , a = 10.7941(12), b = 11.4759(14), c = 12.5263(13), α = 115.350(4)°, β = 102.957(4)°, γ = 100.999(4)° for II. Crystal packings I and II have the same structure of molecules. Crystal structures I and II are molecular and consist of discrete Cu(fod)2 molecules. Temperature dependences for saturated vapor pressure have been obtained by flow method for liquid and crystalline (phase I) Cu(fod)2 in the range 314–393 K. Thermal stability of the compound is determined, thermodynamic parameters of sublimation and evaporation have been established.

The heat capacity of copper bis-dipivaloylmethanate complex (Cu(C11H19O2)2 or Cu(dpm)2; CAS no. 14040-05-2) in the 5.440–313.271 K range of temperatures is measured via adiabatic calorimetry. The functional behavior of the heat capacity in the studied range of temperatures does not exhibit any anomaly that could be attributed to phase transitions. The heat capacity data are used to calculate entropy, enthalpy increment, and reduced Gibbs energy in the 0–310 K range of temperatures. Based on this analysis, a universal description of heat capacity is proposed for metal dipivaloylmethanates in a wide range of temperatures. The description can be used to calculate the thermodynamic characteristics of objects from this isoligand group of metal beta-diketonates that have yet to be studied.

С целью определения влияния размера заместителя в β-дикетонатном лиганде на строение и термические свойства летучих комплексов Ni(II), проведен синтез соответствующего производного для гептандиона-3,5 (Hhd). С помощью РСА изучено строение [Ni3(hd)6], а также его производных [Ni4(OMe)4(hd)4(MeOH)4] и [Ni3(OH)(hd)5(H2O)]2. Трехъядерный комплекс подобен простейшему β-дикетонатному аналогу, полученная тетраядерная структура характерна для смешаннолигандных алкокси-β-дикетонатных комплексов двухвалентных металлов, тогда как гексаядерная – является уникальной. С помощью термогравиметрии проведено сравнение термических свойств β-дикетонатов Ni(II) в ряду L = RC(O)CHC(O)R, R = Me, Et, tBu.

The crystal structure of new isostructural complex Tb(thd)3 (1), Ho(thd)3 (2) (sp. gr. Pmn21) and Tb(thd)3 (3), Dy (thd)3 (4), Er(thd)3 (5), Yb(thd)3 (6) (sp. gr. Pna21) are determined. The crystal structures of 1-6 are molecular and consist of discrete monomeric Ln(thd)3 molecules (Ln = Tb, Ho, Dy, Er, Yb). The samples of Ln(thd)3 in the solid state have been investigated over the temperature range from 120 to 300 K using differential scanning calorimetry. DSC curves Ln(thd)3 exhibit a single endothermic peak of the crystal-to-crystal reversible phase transition. First-order phase transition is accompanied by an abrupt change in the volume of the unit cell. The quantum chemical calculations allow one to conclude that the electronic structures of the three modifications for Tb tris-2,2,6,6-tetramethylheptane-2,4-dionates are some different. It has been shown that for Tb(III) complexes with thd-ligands the modification I is energetically more stable.

The influence of the size of the β-diketonate ligand substituent on the structure and thermal properties of volatile Ni(II) complexes is determined. To this aim, a corresponding heptanedione-3.5 (Hhd) derivative is prepared. The structures of [Ni3(hd)6] and its derivatives [Ni4(OMe)4(hd)4(MeOH)4] and [Ni3(OH) (hd)5(H2O)]2 are studied by XRD. The trinuclear complex is similar to its simplest β-diketonate analogue. Such a tetranuclear structure is typical for mixed-ligand alkoxy-β-diketonate divalent metal complexes, whereas the hexuclear structure is unique. Thermal properties of Ni(II) β-diketonates in the series L = RC(O)CHC(O)R, R = Me, Et, tBu are compared by the thermogravimetry method.

Проведено рентгеноструктурное исследование монокристаллов Fe(dpm)3 (dpm – дипивалоилметанат) в интервале температур 90-365 K. Обнаружена новая кристаллическая модификация в интервале 90-100 K (пр. гр. Р, Z = 8), подтвержден фазовый переход при 230 K (пр. гр. Р, Z = 4). В диапазоне 250-365 K относительное увеличение параметров моноклинной ячейки (пр. гр. C2/c, Z = 8) составило Δa/a = 0.67, Δb/b = 1.16 и Δc/c = 0.47 %, угол  уменьшился на 3,3 %. В интервале 90-365 K относительное увеличение объема, приходящегося на одну молекулу, составило 6.65 %, причем средние значения расстояний Fe-O и хелатных углов O-Fe-O практически не изменились. Построены поверхности Хиршвельда для структур при температурах: 90, 130, 250 и 365 K. Изучены слои Fe(dpm)3, полученные напылением в вакууме (PVD) и кристаллизацией раствора при центрифугировании (spin coating) на разных неорганических подложках, установлена ориентация и проведен анализ особенностей структуры в направлениях [100] и [001].

Five volatile lithium beta-diketonates: Li(tmhd) (1), Li(pta) (2), LiL (3), LiLF (4), Li(tmha) (5) (tmhd = 2,2,6,6tetramethyl-heptane-3,5-dionate, pta = 1,1,1-trifluoro-5,5-dimethyl-hexane-2,4-dionate, L = 2-methoxy-2,6,6trimethyl-heptane-3,5-dionate, LF = 1,1,1-trifluoro-5-methoxy-5-methyl-hexane-2,4-dionate, tmha = 2,2,6,6tetramethyl-heptane-3-imino-5-onate) and lithium alkoxide Li(OtBu) (6) were examined by combination of several complementary methods to study their thermal behavior in solid and gas phase and to check their suitability as precursors for chemical vapor deposition of Li-containing films. The best storage stability was observed for 3 and 4. Thermal gravimetric analysis and vacuum sublimation test were used to compare stability of the complexes under vaporization. In situ mass spectrometry was used to study the gas phase composition and the surface decomposition chemistry. Diketonate complexes 1, 3-5 passed into the gas phase as tetranuclear particles. Upon further heating, they split into binuclear species. The binuclear species thermolysis is responsible for the film deposition. The vapor thermal stability in oxygen increases in the row 3 > 1>5 > 2>4 > 6. CVD films obtained at 500 degrees C in the presence of oxygen using 1, 3 and 5 consisted of Li2CO3. LiF films can be obtained using 2, while 4 allow one to obtain the Li metal films in the oxygen presence on both Si and Pt/Si substrates.

Kinetic and energy characteristics of reversible intermolecular processes for [Pr(DPM) 3 ], [Pr(DPM) 3 (18-crown-6)], and [(Pr(DPM) 3 ) 2 (18-crown-6)] complexes in the CDCl 3 solution (DPM=dipivaloylmethane anion) are characterized by dynamic 1 H NMR.

A variety of physicochemical means are used to synthesize and characterize a sample of the dimer lutetium pivaloyltrifluoroacetonate ([Lu(C 8 H 10 F 3 O 2 ) 3 ] 2 ) complex. The thermal stability of this complex is studied via differential thermal analysis (DTA) and thermogravimetry (TG) in the region of 300–505 K, and its temperature of melting is determined. Experimental heat capacity data are measured in the region of 195‒410 K for the first time via differential scanning calorimetry. No heat capacity anomalies associated with phase transitions are revealed below the melting point. Smoothed values are calculated for the regular heat capacity of [Lu(C 8 H 10 F 3 O 2 ) 3 ] 2 in the region of 195–443 K.

Методом динамического 1Н ЯМР охарактеризованы кинетические и энергетические характеристики обратимых межмолекулярных процессов в комплексах [Pr(ДПМ)3], [Pr(ДПМ)3(18-краун-6)] и [(Pr(ДПМ)3)2(18-краун-6)] в растворе CDCl3, где ДПМ= анион дипивалоилметана.

Complexes [(Pr(DPM)3)2], [Pr(DPM)3(18-crown-6)], [(Pr(DPM)3)2(18-crown-6)], [Pr(DPM)(PTA)(18-crown-6)]+ and the temperature sensitivity of paramagnetic lanthanidine-induced shifts of these complexes in CDCl3 solution are characterized by 1H NMR. The NMR methods are used to estimate the possibility of forming inclusive complexes in CDCl3 solution upon the interaction of lanthanide tris-β-diketonates with 18-crown-6 in the case of a more branched ligand than PTA (e.g., DPM). Upon the interaction of [(Pr(DPM)3)2] and 18-crown-6, the [Pr(DPM)3(18-crown-6)] forms prevail in solution. The obtained results indicate that the studied coordination compounds can be considered as 1H NMR paramagnetic lanthanide probes for local temperature control in organic solutions using the analysis of paramagnetic lanthanidine-induced shifts.

Thermogravimetry, differential scanning calorimetry, and flow methods were used to investigate thermal properties of a series of cobalt(II) β-iminoketonates [R2C(NR1)CHC(O)R2]. The consecutive order of their volatility was determined. The complexes do not decompose up to melting and do not undergo phase transitions. For the complex (R1 = Н, R2 = Me) the temperature dependence of sublimation ln (p/p0) = 32.02 ‒ 16822/T(K) at 402.6‒433.7 K was measured and the values of ΔsublH°Т* = 140±4 kJ/mol and ΔsublS°Т* = 266±10 J/(K·mol) were calculated.

The crystal structure of new isostructural complex Y(thd)(3) (I), Ho(thd)(3) (II), Tm(thd)(3) (III) and Lu(thd)(3) (IV) are determined: space group Pna2(1), Z = 8 (a = 41.956(8) angstrom, b = 17.837(4) angstrom, c = 9.742(2) angstrom, V = 7291(3) angstrom(3) for I; a = 41.778(2) angstrom, b = 17.8045(6) angstrom, c = 9.6862(3) angstrom, V = 7204.9(4) angstrom(3) for II; a = 41.884(5) angstrom, b = 17.758(2) angstrom, c = 9.672(1) angstrom, V = 7193.7(2) angstrom(3) for III, a = 41.942(8) angstrom, b = 17.712(4) angstrom, c = 9.711(2) angstrom, V = 7214(2) angstrom(3) for IV). The crystal structures of I-IV are molecular and consist of discrete monomeric Ln(thd)(3) molecules (Ln = Y, Ho, Tm, Lu). The highest quantum yields of luminescence are obtained for Tb(thd)(3) (77%), [Tb(thd)(3)](2) (25%) and Dy(thd)(3) (5%), [Dy(thd)(3)](2) (0.4%). Thermogravimetric investigations show that the volatility of complexes increases from Yb(thd)(3) to Pr(thd)(3). Melting points of the complexes are close to the known literature data. The complex compounds we synthesized were characterized by NMR in a CDCl3 solution. Quantum chemical calculations are shown that the phase of dimeric molecules is energetically more stable for the Y(III) complexes with thd-ligands. (C) 2021 Elsevier Ltd. All rights reserved.

Interatomic interactions and charge state of atoms in hexanuclear complex [Cu-6(hfa)(4)(dpm)(4)(OH)(4)] have been studied by the methods of quantum chemistry and X-ray photoelectron spectroscopy (XPS). The shape and energy position of the Cu2p(3/2)-lines indicate that all copper atoms state could be interpreted as Cu2+. It was also analyzed the quantum chemical and XPS data on atomic charge distribution for monoligandic bis-beta-diketonate Cu(hfa)(2) and Cu(dpm)(2) complexes. The comparison of calculated and experimental data for monoligandic and hexanuclear complexes revealed the electronic density redistribution on the oxygen and copper atoms in 1 due to the charge transfer interaction between Cu(hfa)(2)- and Cu(dpm)-fragments with participation of the bridging OH-groups, which was confirmed by NBO analysis. (C) 2021 Elsevier B.V. All rights reserved.

Синтезирована серия трис-дипивалоилметанатов Ln(III) с фенантролином состава Ln(thd)3Phen (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb). Установлено, что все аддукты изоструктурны с ранее известными комплексами La(thd)3Phen, Tb(thd)3Phen и Dy(thd)3Phen. Определены кристаллические структуры комплексов Sm(thd)3Phen (I) и Eu(thd)3Phen (II) при 150(2) K (пр. гр. P-1, a = 10.8590(5) Å, b = 12.3049(6) Å, с = 18.4479(10) Å, α = 80.210(2)°, β = 87.499(2)°, γ = 68.799(2)°, V = 2264.3(2) Å3, Z = 2; пр. гр. P-1, a = 10.8788(3) Å, b = 12.3009(3) Å, с = 18.4309(5) Å, α = 80.3644(9)°, β = 87.5440(10)°, γ = 68.7376(8)°, V = 2265.7(1) Å3, Z = 2 соответственно). Кристаллические структуры I и II являются молекулярными и состоят из изолированных молекул Ln(thd)3Phen (Ln = Sm(III), Eu(III)). Наибольшие квантовые выходы люминесценции для данной серии аддуктов установлены для Eu(thd)3Phen (10 %) и Sm(thd)3Phen (1.5 %). Термогравиметрические исследования (ТГ) показали, что летучесть аддуктов слабо уменьшается от Pr(thd)3Phen до Yb(thd)3Phen; их точки плавления близки к известным по литературным данным.

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.

Ferrous cysteinate nanoparticles were obtained and characterized for the first time and tested as a feed additive on chickens.

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 series of Ln(III) tris-dipivaloylmethanates with phenanthroline with the composition Ln(thd)3Phen (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) is synthesized. It is found that all adducts are isostructural with previously known La(thd)3Phen, Tb(thd)3Phen, and Dy(thd)3Phen complexes. Crystal structures of Sm(thd)3Phen (I) and Eu(thd)3Phen (II) complexes are determined at 150(2) K (space group $$P\overline 1 $$, a = 10.8590(5) Å, b = 12.3049(6) Å, c = 18.4479(10) Å, α = 80.210(2)°, β = 87.499(2)°, γ = 68.799(2)°, V = 2264.3(2) Å3, Z = 2; space group $$P\overline 1 $$, a = 10.8788(3) Å, b = 12.3009(3) Å, c = 18.4309(5) Å, α = 80.3644(9)°, β = 87.5440(10)°, γ = 68.7376(8)°, V = 2265.7(1) Å3, Z = 2 respectively). Crystal structures of I and II consist of isolated Ln(thd)3Phen molecules (Ln = Sm(III), Eu(III)). The highest luminescence quantum yields for this series of adducts are established for Eu(thd)3Phen (10%) and Sm(thd)3Phen (1.5%). Thermogravimetric studies show that the volatility of adducts weakly increases from Pr(thd)3Phen to Yb(thd)3Phen. Their melting points are close to the reported data.