Two new compounds, trichloro[O-bis(2-hydroxyethyl)ammonium] manganese(ii), {Mn[(HOCH2CH2)2NH2]Cl3}n (1), and N-(2-hydroxyethyl)-N-methylammonium aquatrichloromanganate(II), [CH3NH2CH2CH2OH][Mn(H2O)Cl3] (2), were synthesized. The crystal structures of the new compounds were determined by single-crystal X-ray diffraction. Both structures contain similar chains composed of (MnOCl5) octahedra. In the structure of 1, the manganese atom is coordinated by the OH group of the cation; in the structure of 2, the manganese atom is coordinated by a water molecule. There are different hydrogen bond systems in the structure of 1 due to disorder of OH groups of the cation. The melting points and enthalpies of the synthesized compounds evaluated by DSC are 162 °C and 17.3 kJ mol−1 for compound 1 and 30 °C and 16.9 kJ mol−1 for compound 2, respectively. Compound 1 is a chain coordination polymer, while compound 2 is an ionic liquid with a polynuclear anion.

Cobalt triflate hexahydrate [Co(H 2 O) 6 ](CF 3 SO 3 ) 2 ( I ) is crystallized from aquos solution. The dehydration of salt I at 200°C in an argon flow affords anhydrous salt Co(CF 3 SO 3 ) 2 ( II ). The crystal structures of compounds I and II are determined from single crystal and powder X-ray diffraction data, respectively. Compound I is isostructural to [Ni(H 2 O) 6 ](CF 3 SO 3 ) 2 and crystallizes in the space group P 3̅ m 1, а = 7.3914(16), с = 8.704(2) Å, V = 411.8(2) Å 3 , Z = 1. The structure of compound II (space group R 3̅ , а = 4.9996(1), с = 31.3137(8) Å, V = 677.86(3) Å 3 , Z = 3) belongs to the structural type M(CF 3 SO 3 ) 2 , where M = Mg, Ca, and Zn. In the structures of both compounds, the cobalt atoms are in the octahedral environment of the oxygen atoms belonging to the water molecules ( I ) or triflate groups ( II ). In compound I , the [Co(H 2 O) 6 ] 2+ cations localized in the nodes of a regular triangular network are linked with the (CF 3 -SO 3 ) – anions via hydrogen bonds to form layers parallel to the (001) plane. When compound I is dehydrated to form compound II , the [CoO 6 ] octahedra are coupled via the μ 3 -CF 3 SO 3 group with the retention of the layered structure. The synthesized compounds are characterized by IR spectroscopy, TG/DTA/MS. The results of studying the magnetic properties of compounds I and II indicate no magnetic ordering at low temperatures and correspond to the paramagnetic behavior of compounds I and II at high temperatures with a considerable contribution of the spin-orbital interaction to the effective magnetic moment of the cobalt atom.

Metal-containing ionic liquids composed of the 2,8-dioxo-5-azoniaspiro[4.5]decane (MorphOx) and 2-oxo-5-azoniaspiro[4.4]nonane (PyrOx) spiro cations and tetrachlorometallate anions MCl42-(M = Mn, Ni, Co) were synthesized and studied by X-ray diffraction (CIF file CCDC nos. 2033482 (Morph-Ox(2)CoCl(4)), 2033483 (PyrOx(2)CoCl(4)), 2033484 (PyrOx(2)MnCl(4)), and 2033485 (PyrOx(2)NiCl(4))). The compounds PyrOx(2)MCl(4) are isostructural. The phase transition temperatures of the compounds were determined by differential scanning calorimetry.

Protic metal-containing ionic liquids with the diethanolammonium cation (HO–CH2–CH2)2$${\text{NH}}_{{\text{2}}}^{ + }$$ (DEAH+) and anions $${\text{FeCl}}_{{\text{4}}}^{-}$$ and $${\text{CoCl}}_{{\text{4}}}^{{{\text{2}}-}}$$ (DEAHFeCl4 (I), (DEAH)2CoCl4 (II)) are synthesized. The crystal structures of compounds I and II are determined by X-ray structure analysis (CIF files CCDC nos. 1957208 (I) and 1957189 (II)). Compound I has a layered structure. The layer consists of the DEAH+ cations with the disordered system of hydrogen bonds and attached $${\text{FeCl}}_{{\text{4}}}^{-}$$ anions. The structure of compound II represents a three-dimensional framework consisting of the DEAH+ cations and $${\text{CoCl}}_{{\text{4}}}^{{{\text{2}}-}}$$ anions linked by hydrogen bonds. The thermal analysis shows that the melting points of compounds I (45°С) and II (55°С) are lower than 100°С, the enthalpy of melting of compound I is higher than that of compound II, and the decomposition temperature of compound II (210°С) is higher than that of compound I (128°C).

Bimetallic trichloroacetates of the composition Cs[M(CCl3COO)3(H2O)3], where (I: M = Co, II: Ni) were synthesized. The structures of these compounds have been determined by the single crystal X-ray diffraction. The compounds are isostructural and crystallize in the trigonal system, sp.gr. $$ R\overline{3} $$ . а = b = 10.5770(6), c = 32.8213(2) Å, α = β = 90°, γ = 120°, Z = 6, V = 3179.9(4) Å3 (for Со compound), а = b = 10.5404(4), c = 32.7116(7) Å, α = β = 90°, γ = 120°, Z = 6, V = 3147.4(2) Å3 (for Ni compound). The structure contains [M(CCl3COO)3(H2O)3] anions, where (M = Co, Ni). The d-metal atom is located in the distorted octahedral environment of oxygen atoms in the anion. These compounds have nearly the same IR spectra. The thermal stability of the compounds was studied. The thermal behavior of these compounds is similar to each other, but the difference is in the stage of loss of crystallization water—for the nickel compound, this process starts at 20 °C higher than for the cobalt compound. The high-temperature process of the transition of metal chlorides to the gas phase differs: for the cobalt compound, the mass loss begins at 600 °C, whereas for the nickel compound, the mass loss begins at 720 °C. The compounds obtained are the first examples of alkaline metal—transition metal trichloroacetates.

Dicationic ionic liquid (IL) dibutyltetramethylethylenediammonium tetrafluoridoborate was synthesized for the first time by quaternization followed by ion exchange. The chemical composition was confirmed by 1H, 19F, and 13C nuclear magnetic resonance (NMR) spectroscopy. The crystal structure of the IL under discussion was determined from single crystal diffraction and can be described in monoclinic syngony with P21/c space group. Using thermal analysis and mass spectrometry, thermal stability of this IL as well as possible directions of its destruction was analyzed. Melting point for this liquid was determined by simultaneous thermal analysis as 135 °C. The electrochemical stability range for this ionic liquid was find to be nearly symmetrical accordingly to cyclic voltammetry and estimated as 3.75 V.

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.

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.

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.

Data on the syntheses and structures of trifluoroacetates of 3d elements mainly based on our results are reviewed. Specific features of the coordination chemistry of mono-, oligo-, and polynuclear trifluoroacetate complexes are successively considered. Special attention is given to oxo- and fluorotrifluoroacetates containing the trinuclear triangular fragment as a structural unit. Structural features of trifluoroacetates compared to other carboxylates are discussed.

Silicon nanocrystals stabilized by an ionic liquid, dimethylimidazolium iodide, were synthesized by chemical reduction of SiBr4 with metallic Na in an organic solvent, diglyme. The nanoparticles were crystalline with a diamond cubic lattice and average size of 3.5 nm. Solid state 13C- and 29Si-NMR CP MAS spectra indicate the formation of imidazolium carbene, which ligates the Si atoms at the surface of the nanoparticles. The synthesized Si nanoparticles exhibit photoluminescence with an emission maximum in the red spectral range when excited at 320 nm. The origin of this luminescence is suggested to be mainly related to quantum confinement.

Sodium reduction of a mixture of tetrabromosilane with imidazole ionic liquids in organic solvents gives dispersions of silicon nanoparticles stabilized by carbene ligands. It was shown that the size of silicon nanoclusters depends on the size of substituents at nitrogen atoms of 1,3-dialkylimidazol-2-ylidenes.

Mesoporous aluminum hydroxides and oxides were synthesized using ionic liquids (ILs) as templates. The influence of various factors (the nature of the IL, pH, ultrasonication, surfactants, reagent ratio, and the nature of the aluminum precursor) on the specific surface area and pore volume was analyzed.

Thulium trifluoroacetate compounds have been synthesized, Tm(CF3COO)3 · 3H2O (I) and Tm2(CF3COO)6 · 2CF3COOH · 3H2O (II). The structure of I has been refined by the Rietveld method on the basis of the structural data for Cd(CF3COO)3 · 3H2O. The structure of II has been solved in a single-crystal X-ray diffraction study. Compound I has been studied by thermal analysis. Crystals of I and II are monoclinic: for Ia = 9.062(2) Å, b = 18.678(3) Å, c = 9.687(2) Å, β = 113.93(1)°, Z = 2, space group P21/c, R1 = 0.062; for IIa = 8.560(4) Å, b = 19.866(5) Å, c = 20.813(7) Å, β = 101.69(4)°, Z = 8, space group C2/c, R1 = 0.0392. In the molecular structure of I, thulium atoms are bonded in pairs through four bridging trifluoroacetate anions to form dimers. The coordination polyhedron of the thulium atom also includes the three O atoms of the water molecules and the O atom of the monodentate trifluoroacetate group; the coordination number of the thulium atom is eight. In the chain structure of II, there are two crystallographically independent thulium atoms with coordination numbers 8 and 9. The coordination polyhedra of the Tm(1) and Tm(2) atoms are a distorted monocapped tetragonal antiprism and a distorted tetragonal antiprism, respectively. The Tm-O bond lengths are in the range 2.28(1)–2.85(2) Å. The thulium atoms are bound into chains through carboxylate groups. These chains are linked into layers through hydrogen bonds.

Prolonged exposure of glasses to concentrated solutions of selenic acid was found to result in formation of calcium hydrogen selenates Ca(HSeO 4 ) 2 . H 2 O and CsCa(HSeO 4 ) 3 ; their compositions and structures were determined by X-ray crystallography. The structures of these compounds are three-dimensional frameworks consisting of metal cation polyhedra and tetrahedral HSeO 4 groups and including water molecules (in the case of Ca(HSeO 4 ) 2 . H 2 O). The HSeO - 4 anions and water molecules are hydrogen-bonded to form ribbons in the first compound and branched chains in the second one.

The possibility of reproducing regularities of static mutual influence of ligands in complexes of Period V and VI elements of the Periodic Table (Pd, Sn, Sb, Pt, Pb) using the density functional theory (DFT) calculations is studied. Relativistic effects are taken into account by means of the Dirac equation approximation (zero-order regular approximation, ZORA). The calculations reproduced trans-influence in Pt complexes and trans-shortening and cis-elongation in the nontransition metal complexes. At the same time, Pb chloride complexes and Sn iodide complexes exhibit substantial differences between experimental and calculation bond lengths. When solvation was accounted for by COSMO method, DFT calculations reproduce the relative stability of the cis- and trans-Pt(NH3)2X2 complexes (X is halogen) and of the sulfur-containing Ni and Pd chelate complexes. The calculated geometry of the cis-Pt(NH3)2X2 molecule noticeably differs from the experimental geometry due to the overestimated strength of intramolecular N-H···X hydrogen bonds.

Single crystals of rare earth (RE) selenates of the compositions Nd(HSeO4)3, Sm(HSeO4)3, and Nd2(SeO4)3 · 5H2O are synthesized and studied by X-ray diffraction analysis at T = 297 and 180 K. It is established that Nd and Sm hydrogen selenates are isostructural to one another and to the corresponding hydrogen sulfates. Neodymium selenate pentahydrate is not isostructural to the analogous RE sulfates, although their structural motifs are similar.