Synthesis, characterization and thermal properties of new aromatic quaternary ammonium bromides: precursors for ionic liquids and complexation studies

Series of new aromatic R₂R′₂N⁺Br⁻ (R=benzyl, 4-methylbenzyl, 2-phenylethyl, 3-phenylpropyl; R′=ethyl, methyl, isopropyl) or RR′₂NH⁺Br⁻-type (R=benzyl, R′=isopropyl) quaternary ammonium bromides were prepared by using novel synthetic route in which a formamide (N,N-diethylformamide, N,N-dimethylformamide, N,N-diisopropylformamide) is treated with aralkyl halide in presence of a weak base. The compounds were characterized by ¹H-NMR and ¹³C-NMR spectroscopy and mass spectrometry. Structures of the crystalline compounds were determined by X-ray single crystal diffraction, and in addition the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bulk material. Three of the compounds crystallized in monoclinic, two in orthorhombic and one in triclinic crystal system, showing ion pairs, which are interconnected by weak hydrogen bonds and weak π-π interactions between the phenyl rings. Three of the compounds appeared as viscous oil or waxes. Finally, TG/DTA and DSC methods were used to analyze thermal properties of the prepared compounds. The lowest melting points were obtained for diethyldi-(2-phenylethyl)ammonium bromide (122.2 °C) and for diethyldi-(3-phenylpropyl)-ammonium bromide (109.1 °C). In general, decomposition of the compounds started at 170-190 °C without identifiable cleavages, thus liquid ranges of 30-70 °C were observed for some of the compounds.     

二甲基烯丙基胺/溴代烷烃系列季铵盐的合成与表征

以溴代烷与二甲基烯丙基胺(DMAA)为原料合成了二甲基烯丙基类季铵盐;探讨了反应温度、原料配比、反应时间及溶剂对反应产率的影响,确定了最佳合成条件;并采用红外光谱仪、核磁共振谱仪(1 H NMR)及质谱仪表征了产物的结构.     

Crystal structures of the La3AgSnSe7 and R3Ag1−δSnS7 (R=La, Ce; δ=0.18−0.19) compounds

The crystal structures of new quaternary compounds La₃AgSnSe₇ (space group P6₃, Pearson symbol hP24, a=1.0805(4) nm, c=0.6245(1) nm, R1=0.0315), La₃Ag_0.82SnS₇ (space group P6₃, Pearson symbol hP23.64, a=1.0399(1) nm, c=0.6016(1) nm, R1=0.0149) and Ce₃Ag_0.81SnS₇ (space group P6₃, Pearson symbol hP23.62, a=1.0300(1) nm, c=0.6002(1) nm, R1=0.0151) were determined by means of X-ray single crystal diffraction. Structural investigations of the R₃Ag_1−δSnS₇ (R=La, Ce; δ=0.18-0.19(1)) compounds at 450 and 530 K were performed. Low temperature data (12 K) for Ce₃Ag_0.81SnS₇ were also collected. The nearest neighbours of the La(Ce), Ag and Sn atoms are exclusively Se(S) atoms. The latter form distorted trigonal prisms around the La(Ce) atoms, and distorted tetrahedrons around the Sn atoms. The Ag (Ag1) atoms have triangular surroundings: they are located very close to the planes built of three Se(S) atoms. The Ag2 atoms in the structures of the La₃Ag_0.82SnS₇, Ce₃Ag_0.81SnS₇ compounds are located practically in the centres of trigonal antiprisms. The pseudo-potentials determined through the Ag atoms show relatively low barrier between two nearest positions which decreases when temperature rises.     

Synthesis, crystal structure and thermal behavior of Sr3B2SiO8 borosilicate

Single crystals of Sr₃B₂SiO₈ were obtained by solid-state reaction of stoichiometric mixture at 1200 °C. The crystal structure of the compound has been solved by direct methods and refined to R1=0.064 (wR=0.133). It is orthorhombic, Pnma, a=12.361(4), b=3.927(1), c=5.419(1) Å, V=263.05(11) Å³. The structure contains zigzag pseudo-chains running along the b axis and built up from corner sharing (Si,B)−O polyhedra. Boron and silicon are statistically distributed over one site with their coordination strongly disordered. Sr atoms are located between the chains providing three-dimensional linkage of the structure.The formation of Sr₃B₂SiO₈ has been studied using annealing series in air at 900-1200 °C. According powder XRD, the probe contains pure Sr₃B₂SiO₈ over 1100 °C. The compound is not stable below 900 °C. In the pseudobinary Sr₂B₂O₅-Sr₃B₂SiO₈ system a new series of solid solutions Sr_3−xB₂Si_1−xO_8−3x (x=0-0.9) have been crystallized from melt. The thermal behavior of Sr₃B₂SiO₈ was investigated using powder high-temperature X-ray diffraction (HTXRD) in the temperature range 20-900 °C. The anisotropic character of thermal expansion has been observed: α_a= −1.3, α_b=23.5, α_c=13.9, and α_V=36.1×10⁻⁶ °C⁻¹ (25 °C); α_a= −1.3, α_b=23.2, α_c=5.2, and α_V=27.1×10⁻⁶ °C⁻¹ (650 °C). Maximal thermal expansion of the structure along of the chain direction [0 1 0] is caused by the partial straightening of chain zigzag. Hinge mechanism of thermal expansion is discussed.     

Structure determination from powder diffraction data and thermal behaviour of layered lead nitrate oxalate hydrate, Pb2(NO3)2(C2O4).2H2O

The mixed lead nitrate oxalate, Pb₂(NO₃)₂(C₂O₄).2H₂O, has been obtained in a polycrystalline form in the course of a study on precursors of nanocrystalline PZT-type oxides. Its crystal structure has been solved from powder diffraction data collected using a monochromatic radiation from a conventional X-ray source. The symmetry is monoclinic, space group P2₁/c (No. 14), the cell dimensions are a=10.623(2) Å, b=7.9559(9) Å, c=6.1932(5) Å, β=104.49(1)° and Z=4. The structure consists of a stacking of complex double sheets parallel to (1 0 0), forming layers held together by hydrogen bonds. The sheets result from the condensation of PbO₁₀ polyhedra, in which the oxalate and nitrate groups, as well as water molecules, play a major role. The structure is discussed in terms of Pb---O distances, polyhedra shape and lead coordination, with emphasis on the dimensional polymerisation role of water molecules. The thermal behaviour of this layered compound is carefully described from temperature-dependent powder diffraction and thermogravimetric measurements. The enthalpy, Δ_rH=232(3) kJ mol⁻¹, and entropy, Δ_rS=532(8) J K⁻¹ mol⁻¹, of the dehydration reaction have been determined. The high value of Δ_rH demonstrates that the water molecules are strongly bonded in the structure. The complex decomposition proceeds through the crystallisation and decomposition of Pb(NO₃)₂(C₂O₄) into Pb(NO₃)₂ and PbC₂O₄, and, finally, various lead oxides.     

Synthesis and properties of long-chain quaternary ammonium hydroxides

A series of long-chain quaternary ammonium hydroxides were synthesized from tertiary amines and confirmed by ~1H NMR and FTIR.Surface properties and pH of these surfactants were investigated.The critical micelle concentrations(CMC) of the synthesized quaternary ammonium hydroxides are lower than the conventional quaternary ammonium surfactants.The micelles shapes of these long-chain quaternary ammonium hydroxides in aqueous solution are spherical at a concentration of 0.1 mol/L.The pH values of the synthesized quaternary ammonium hydroxides are 12.25-12.51.     

Synthesis, crystal structure and thermal behavior of a novel oxoborate SrBi2B4O10

A new compound, SrBi₂B₄O₁₀, has been grown by cooling a melt with the stoichiometric composition. It is triclinic, P−1, a=6.819(1), b=6.856(1), c=9.812(2) Å, α=96.09(1), β=109.11(1), γ=101.94(1)°, V=416.5(1) Å³, Z=2. The crystal structure of the compound has been solved by direct methods and refined to R₁=0.050 (wR₂=0.128). The structure contains Bi-O pseudolayers build up from Bi-O chains involving oxocentred OBi₃ triangles. Sr atoms and [B₄O₉]⁶⁻ isolated anions (4B:3Δ□:<2Δ□>Δ) are located between the Bi-O packages.The thermal treatment as well as DSC experiment showed that the compound melts above 800 °C presumably according to the peritectic reaction: SrBi₂B₄O₁₀ ↔ SrB₂O₄+SrB₄O₇+ Liquid. According to high-temperature X-ray powder diffraction study thermal expansion of SrBi₂B₄O₁₀ structure is anisotropic (α₁₁=13, α₂₂=9, α₃₃=2, α_V=24×10⁻⁶ °C⁻¹).     

Phase equilibria in systems Ce-M-Sb (M=Si, Ge, Sn) and superstructure Ce12Ge9−xSb23+x (x=3.8±0.1)

Phase relations in the ternary systems Ce-M-Sb (M=Si, Ge, Sn) in composition regions CeSb₂-Sb-M were studied by optical and electron microscopy, X-ray diffraction, and electron probe microanalysis on arc-melted alloys and specimens annealed in the temperature region from 850 to 200 °C. The results, in combination with an assessment of all literature data available, were used to construct solidus surfaces and a series of isothermal sections. No ternary compounds were found to form in the Ce-Si-Sb system whilst Ce₁₂Ge_9−xSb_23+x (3.3<x<4.2) and CeSn_xSb₂ (0.1<x<0.8) participate in phase equilibria in the composition region investigated. Crystallographic parameters for the ternary compound Ce₁₂Ge_9−xSb_23+x (x=3.8±0.1) were determined from X-ray single crystal and powder diffraction. For the binary system Ge-Sb a eutectic was defined L⇔(Ge)+(Sb) at 591.6 °C and 22.5 at%. Ge EPMA revealed a maximal solubility of 6.3 at% Ge in (Sb) at the eutectic temperature.     

Crystal structure of Ca2Ln3Sb3O14 (Ln=La, Pr, Nd and Y): A novel variant of weberite

The crystal structures of Ca₂Ln₃Sb₃O₁₄ (Ln=La, Pr, Nd and Y) and Ca₂Sb₂O₇ at room temperature were refined by the Rietveld method using combined X-ray and neutron powder diffraction data. Ca₂Sb₂O₇ adopts the weberite structure having the space group Imma. The structures of Ca₂Ln₃Sb₃O₁₄ are, however, neither the orthorhombic nor the tetragonal chiolite as has been suggested previously. They crystallize in the monoclinic space group I2/m11 belonging to a hitherto unknown type of deformation of the parent (orthorhombic) weberite structure.     

Ionic conductivity, structural and thermal properties of pure and Sr doped Y2Ti2O7 pyrochlores for SOFC

In the present study, SrO doped Yttrium titanate pyrochlore was synthesized using solid state reaction technique. The sintering characteristics, crystal structure, thermal and conductivity behavior of doped and undoped pyrochlores have been studied to find their suitability in solid oxide fuel cells (SOFC). The as-prepared samples were characterized using X-ray diffraction (XRD), Fourier-Transform-Infrared spectroscopy (FT-IR), thermal-gravimetric analysis (TGA) and ac conductivity up to 900 °C. The results are discussed in light of oxygen vacancy formation and structural disordering. Undoped and doped yttrium titanate with SrO (x = 0.1) exhibits single Y₂Ti₂O₇ phase with relative density of 94%. It was observed that further doping of SrO (x = 0.2–0.4) leads to formation of Y₂Ti₂O₇ phase along with SrTiO₃ phase. Excessive SrO (x = 0.4) results in increase in ionic conductivity to 1.50 × 10⁻¹ S cm⁻¹ whereas it impedes the densification process with relative density of 85%.     

On phase equilibria and crystal structures in the systems Ce-Pd-B and Yb-Pd-B. Physical properties of R2Pd13.6B5 (R=Yb, Lu)

Phase equilibria and crystal structures of ternary compounds were determined in the systems Ce-Pd-B and Yb-Pd-B at 850 °C in the concentration ranges up to 45 and 33 at% of Ce and Yb, respectively, employing X-ray single crystal and powder diffraction. Phase relations in the Ce-Pd-B system at 850 °C are governed by formation of extended homogeneity fields, τ₂-CePd₈B_2−x (0.10<x<0.48); τ₃-Ce₃Pd_25−xB_8−y (1.06<x<1.87; 2.20<y<0.05), and CePd₃B_x (0<x<0.65) the latter arising from binary CePd₃. Crystallographic parameters for the new structure type τ₂-CePd₈B_2−x (space group C2/c, a=1.78104(4) nm, b=1.03723(3) nm, c=1.16314(3), β=118.515(1)° for x=0.46) were established from X-ray single crystal diffraction. The crystal structures of τ₂-CePd₈B_2−x and τ₃-Ce₃Pd_25−xB_3−y are connected in a crystallographic group-subgroup relationship. Due to the lack of suitable single crystals, the novel structure of τ₁-Ce₆Pd_47−xB₆ (x=0.2, C2/m space group, a=1.03594(2) nm, b=1.80782(3) nm, c=1.01997(2) nm, β=108.321(1)°) was determined from Rietveld refinement of X-ray powder diffraction data applying the structural model obtained from single crystals of homologous La₆Pd_47−xB₆ (x=0.19) (X-ray single crystal diffraction, new structure type, space group C2/m, a=1.03988(2) nm, b=1.81941(5) nm, c=1.02418(2) nm, β=108.168(1)°).The Yb-Pd-B system is characterized by one ternary compound, τ₁-Yb₂Pd₁₄B₅, forming equilibria with extended solution YbPd₃B_x, YbB₆, Pd₅B₂ and Pd₃B. The crystal structures of both Yb₂Pd₁₄B₅ and isotypic Lu₂Pd₁₄B₅ were determined from X-ray Rietveld refinements and found to be closely related to the Y₂Pd₁₄B₅-type (I4₁/amd). The crystal structure of binary Yb₅Pd_2−x (Mn₅C₂-type) was confirmed from X-ray single crystal data and a slight defect on the Pd site (x=0.06) was established.The three structures τ₁-Ce₆Pd_47−xB₆, τ₂-CePd₈B_2−x and τ₃-Ce₃Pd_25−xB_8−y are related and can be considered as the packings of fragments observed in Nd₂Fe₁₄B structure with different stacking of common structural blocks.Physical properties for Yb₂Pd_13.6B₅ (temperature dependent specific heat, electrical resistivity and magnetization) yielded a predominantly Yb-4f¹³ electronic configuration, presumably related with a magnetic instability below 2 K. Kondo interaction and crystalline electric field effects control the paramagnetic temperature domain.     

Spectroscopic and thermal properties of FeHg(SCN)4

The preparation and characterization of iron mercury thiocyanate, FeHg(SCN)₄ (abbreviated as FMTC) are described. The spectroscopic properties were characterized by X-ray powder diffraction (XRPD), infrared, Raman and UV-Vis-NIR transmission spectra. The thermal stability and thermal decomposition of FMTC were investigated by means of thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The intermediates and final products of the thermal decomposition were identified by X-ray powder diffraction at room temperature.     

Synthesis and crystal structure of EnH<Superscript>2</Superscript>[IrCl<Superscript>6</Superscript>]

The preparation of EnH²[IrCl⁶] is described. Crystal data for C₂H₁₀Cl₆IrN₂ are: a = 6.8972(11) Å, b = 6.9435(16) Å, c = 7.3354(11) Å; α = 88.269(3)°, β = 65.495(2)°, γ = 60.305(2)°, V = 270.76(9) ų, space group P1, Z = 1, d_calc = 2.864 g/cm³. Crystal chemical analysis of the general motif of the structure was performed by the translation sublattice identification technique. It has been found that complex anions [IrCl₆]^2? follow the nodes of a rather regular rhombohedral subcell with the parameters a_c = 7.1 Å, α_c = 64°.     

Phase formation in the systems Li2MoO4-K2MoO4-Ln2(MoO4)3 (Ln=La, Nd, Dy, Er) and properties of triple molybdates LiKLn2(MoO4)4

Subsolidus phase relations in the systems Li₂MoO₄-K₂MoO₄-Ln₂(MoO₄)₃ (Ln=La, Nd, Dy, Er) were determined. Formation of LiKLn₂(MoO₄)₄ was confirmed in the systems with Ln=Nd, Dy, Er at the LiLn(MoO₄)₂-KLn(MoO₄)₂ joins. No intermediate phases of other compositions were found. No triple molybdates exist in the system Li₂MoO₄-K₂MoO₄-La₂(MoO₄)₃. The join LiLa(MoO₄)₂-KLa(MoO₄)₂ is characterized by formation of solid solutions.Triple molybdates LiKLn₂(MoO₄)₄ for Ln=Nd-Lu, Y were synthesized by solid state reactions (single phases with ytterbium and lutetium were not prepared). Crystal and thermal data for these molybdates were determined. Compounds LiKLn₂(MoO₄)₄ form isostructural series and crystallized in the monoclinic system with the unit cell parameters a=5.315-5.145 Å, b=12.857-12.437 Å, c=19.470-19.349 Å, β=92.26-92.98°. When heated, the compounds decompose in solid state to give corresponding double molybdates. The dome-shaped curve of the decomposition temperatures of LiMLn₂(MoO₄)₄ has the maximum in the Gd-Tb-Dy region.While studying the system Li₂MoO₄-K₂MoO₄-Dy₂(MoO₄)₃ we revealed a new low-temperature modification of KDy(MoO₄)₂ with the triclinic structure of α-KEu(MoO₄)₂¹ (a=11.177(2) Å, b=5.249(1) Å, c=6.859(1) Å, α=112.33(2)°, β=111.48(1)°, γ=91.30(2)°, space group , Z=2).     

Magnetic properties of Fe2P-type R6CoTe2 compounds (R=Gd-Er)

The magnetic structure of the Fe₂P-type R₆CoTe₂ phases (R=Gd-Er, space group P6¯2m) has been investigated through magnetization measurement and neutron powder diffraction. All phases demonstrate high-temperature ferromagnetic and low-temperature transitions: T_C=220 K and T_CN=180 K for Gd₆CoTe₂, T_C=174 K and T_CN=52 K for Tb₆CoTe₂, T_C=125 K and T_CN=26 K for Dy₆CoTe₂, T_CN=60 K and T_N=22 K for Ho₆CoTe₂ and T_CN∼30 K and T_N∼14 K for Er₆CoTe₂.Between 174 and 52 K Tb₆CoTe₂ has a collinear magnetic structure with K₀=[0, 0, 0] and with magnetic moments along the c-axis, whereas below 52 K it adopts a non-collinear ferromagnetic one.Below 60 K the magnetic structure of Ho₆CoTe₂ is that of a non-collinear ferromagnet. The holmium magnetic components with a K₀=[0, 0, 0] wave vector are aligned ferromagneticaly along the c-axis, whereas the magnetic component with a K₁=[1/2, 1/2, 0] wave vector are arranged in the ab plane. The low-temperature magnetic transition at ∼22 K coincides with the reorientation of the Ho magnetic component with the K₀ vector from the collinear to the non-collinear state.Below 30 K Er₆CoTe₂ shows an amplitude-modulate magnetic structure with a collinear arrangement of magnetic components with K₀=[0, 0, 0] and K₁=[1/2, 1/2, 0]. The low-temperature magnetic transition at ∼14 K corresponds to the variation in the magnitudes of the M_Er^K0 and M_Er^K1 magnetic components.In these phases, no local moment was detected on the cobalt site.The magnetic entropy of Gd₆CoTe₂ increases from ΔS_mag=−4.5 J/kg K at 220 K up to ΔS_mag=−6.5 J/kg K at 180 K for the field change Δμ₀H=0-5 T.     

Synthesis and crystal structure of Ln2MGe4O12, Ln=rare-earth element or Y; M=Ca, Mn, Zn

The crystal structure of the promising optical materials Ln₂M²⁺Ge₄O₁₂, where Ln=rare-earth element or Y; M=Ca, Mn, Zn and their solid solutions has been studied in detail. The tendency of rare-earth elements to occupy six- or eight-coordinated sites upon iso- and heterovalent substitution has been studied for the Y_2−xEr_xCaGe₄O₁₂ (x=0-2), Y_2−2xCe_xCa_1+xGe₄O₁₂ (x=0-1), Y₂Ca_1−xMn_xGe₄O₁₂ (x=0-1) and Y_2−xPr_xMnGe₄O₁₂ (x=0-0.5) solid solutions. A complex heterovalent state of Eu and Mn in Eu₂MnGe₄O₁₂ has been found.     

Synthesis of nanostructured LiTi2(PO4)3 powder by a Pechini-type polymerizable complex method

The nanostructured NASICON-type LiTi₂(PO₄)₃ (LTP) material has been synthesized by Pechini-type polymerizable complex method. The use of water-soluble ammonium citratoperoxotitanate (IV) metal complex instead of alkoxides as precursor allows to prepare monophase material. Thermal analyses have been carried out on the powder precursor to check the weight loss and synthesis temperature. X-ray powder diffraction analysis (XRD) has been performed on the LTP powder obtained after heating the powder precursor over a temperature range from 550 to 1050 °C for 2 h. By varying the molar ratio of citric acid to metal ion (CA/Ti) and citric acid to ethylene glycol (CA/EG), the grain size of the LTP powder could be modified. The formation of small and well-crystalline grains, in the order of 50-125 nm in size, has been determined from the XRD patterns and confirmed by transmission electron microscopy.     

Binding of acetylcholine and quaternary ammonium compounds to a C3-symmetric bowl-shaped tripeptide of 2-(3-aminophenoxy)propanoic acids acting as a ditopic receptor

The new tripeptide reported here is composed of (R)-2-(3-aminophenoxy)propionic acid and is a bowl-shaped receptor that simultaneously binds both cations and anions of acetylcholine chloride and benzyltrimethylammonium compounds. An intriguing conformational change of the host was observed in the complexation of the ionic pair, where anion-induced flipping of the amide group on the macrocycle occurred.     

Synthesis and structure analysis of tetragonal Li7La3Zr2O12 with the garnet-related type structure

We have successfully synthesized a high-purity polycrystalline sample of tetragonal Li₇La₃Zr₂O₁₂. Single crystals have been also grown by a flux method. The single-crystal X-ray diffraction analysis verifies that tetragonal Li₇La₃Zr₂O₁₂ has the garnet-related type structure with a space group of I4₁/acd (no. 142). The lattice constants are a=13.134(4) Å and c=12.663(8) Å. The garnet-type framework structure is composed of two types of dodecahedral LaO₈ and octahedral ZrO₆. Li atoms occupy three crystallographic sites in the interstices of this framework structure, where Li(1), Li(2), and Li(3) atoms are located at the tetrahedral 8a site and the distorted octahedral 16f and 32g sites, respectively. The structure is also investigated by the Rietveld method with X-ray and neutron powder diffraction data. These diffraction patterns are identified as the tetragonal Li₇La₃Zr₂O₁₂ structure determined from the single-crystal data. The present tetragonal Li₇La₃Zr₂O₁₂ sample exhibits a bulk Li-ion conductivity of σ_b=1.63×10⁻⁶ S cm⁻¹ and grain-boundary Li-ion conductivity of σ_gb=5.59×10⁻⁷ S cm⁻¹ at 300 K. The activation energy is estimated to be E_a=0.54 eV in the temperature range of 300–560 K.     

Crystal structure and electronic properties of the new compounds U3Co12−xX4 with X=Si, Ge

The new compounds U₃Co_12−xX₄ with X=Si, Ge were prepared by direct solidification of the corresponding liquid phase, followed by subsequent annealing at 1173 K. Single crystal X-ray diffraction carried out at room temperature showed that they crystallize with the hexagonal space group P6₃/mmc (no.194) and the unit-cell parameters a=8.130(5), c=8.537(5) Å and a=8.256(1), c=8.608(1) Å for the silicide and germanide, respectively. Their crystal structure derives from the EuMg_5.2 structure type, and is closely related to the Sc₃Ni₁₁Si₄ and Gd₃Ru_4−xAl_12+x types. For the present compounds, no substitution mechanisms have been observed, the partial occupancy of one Co site results from the presence of vacancies, only. The homogeneity ranges, evaluated by energy dispersive spectroscopy analysis, extend from x=0.0(2) to 0.3(2) and from x=0.0(2) to 1.0(2) for U₃Co_12−xSi₄ and U₃Co_12−xGe₄, respectively. The electronic properties of both compounds were investigated by means of DC magnetic susceptibility and DC electrical resistivity measurements. The U₃Co_12−xX₄ compounds are both Pauli paramagnets with their electrical resistivity best described as poor metallic or dirty metallic behavior.