Structural and luminescence properties of [Ln(ODA)(phen)·4H2O] complexes (Ln=Sm and Dy, ODA=oxydiacetate, phen=1,10-phenanthroline)

Two novel complexes of Sm(III) and Dy(III) with mixed oxydiacetate (ODA) and 1,10-phenanthroline (phen) ligands were synthesized and their structure and luminescence properties were characterized. The complexes of [Ln(ODA)(phen)·4H₂O]Cl·5H₂O [Ln=Sm and Dy] crystallize in the monoclinic space group P2₁/n with Sm: a=12.3401(14) Å, b=16.821(2), c=12.6847(11) Å, β=107.939(10)°, V=2505.0(5) Å³, Z=4 and ρ=1.841 mg/m³, and with Dy: a=12.289(7) Å, b=16.805(6) Å, c=12.705(4) Å, β=108.144(18)°, V=2493.4(19) Å³, Z=4 and ρ=1.786 mg/m³. The complexes of [Sm(ODA)(phen)·4H₂O]⁺ and [Dy(ODA)(phen)·4H₂O]⁺ excited by UV light produce orange red and lightly white emissions, respectively, via the nonradiative energy transfer from phen to the metals. The quantum yield of the sensitized luminescence of [Dy(ODA)(phen)·4H₂O]⁺ (Q=19%) is much greater than that of [Sm(ODA)(phen)·4H₂O]⁺ (Q=1.4%). The luminescence decay times of the complexes were in a few microsecond range and independent of temperature.     

NIR-luminescence from ternary lanthanide [Ho, Pr and Tm] complexes with 1-(2-naphthyl)-4,4,4-trifluoro-1,3-butanedionate

The ligand 1-(2-naphthyl)-4,4,4-trifluoro-1,3-butanedionate (Htfnd) has been employed to synthesize six novel ternary-lanthanide complexes in which the synergic ligands were 1,10-phenanthroline-5,6-dione (dione) and 4,5-diazafluoren-9-one (dafone), respectively. Two series of complexes Ln(tfnd)₃dione and Ln(tfnd)₃dafone (Ln=Ho, Pr, Tm) were obtained. These complexes were characterized by elemental analysis, Fourier Transform Infrared spectra and diffused reflectance. After ligand-mediated excitation, Ln(tfnd)₃dione and Ln(tfnd)₃dafone all show the characteristic NIR luminescence of the corresponding Ln³⁺ ions (Ln=Ho, Pr, Tm). This can be attributed to the efficient energy transfer from ligands to central Ln³⁺ ions, via an antenna effect. The indirect energy transfer in the complexes has been investigated and the differences in the luminescence intensity between Ln(tfnd)₃dione and Ln(tfnd)₃dafone were discussed in detail. The excellent luminescent performances enable these NIR-luminescent complexes to have potential applications in optical amplification operating at 1300 or 1500 nm.     

Structural, vibrational and dielectric properties of new potassium hydrogen sulfate arsenate: K4(SO4)(HSO4)2(H3AsO4)

A new compound, K₄(SO₄)(HSO₄)₂(H₃AsO₄) was synthesized from water solution of KHSO₄/K₃H(SO₄)₂/H₃AsO₄. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å³, Z=2 and ρ_cal=2.466 g cm⁻³. The refinement of 3760 observed reflections (I>2σ(I)) leads to R₁=0.0394 and wR₂=0.0755. The structure is characterized by SO₄²⁻, HSO₄⁻ and H₃AsO₄ tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O₄⁻?S(1)O₄²⁻ and H(12)S(2)O₄⁻?H₃AsO₄). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H₃AsO₄ group to build the chain S(1)O₄?H₃AsO₄ which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K₄(SO₄)(HSO₄)₂(H₃AsO₄) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature.     

Crystal structure and dielectric properties of ordered perovskites Ba2BiSbO6 and BaSrBiSbO6

Neutron powder diffraction studies showed that the ordered perovskites Ba₂BiSbO₆ (BBS) and BaSrBiSbO₆ (BSBS) crystallize in a rhombohedral structure with the space group R3¯. The room-temperature lattice parameters are a=6.0351(2) Å; α=60.202(1)° and a=5.9809(2) Å; α=60.045(2)°, respectively. BBS exhibits a dielectric anomaly near room temperature which may be related to structural transition from the R3¯ to low-temperature monoclinic I2/m symmetry. BSBS shows a dielectric anomaly near 723 K which coincides with a phase transition from the rhombohedral to cubic (Fm3¯m) structure. In contrast to BBS, BSBS does not undergo structural transition below room temperature.     

Solvothermal synthesis, cubic structure and multicolor upconversion emission of ultrasmall monodisperse lanthanide-doped BaYF5 nanocrystals

Lanthanide (Ln³⁺) doped BaYF₅ (Ln=Yb³⁺, Er³⁺, Tm³⁺) nanocrystals (NCs) with a mean size of approximately 10 nm are synthesized by a solvothermal method using oleic acid as a stabilizing agent at 210 °C. The size of BaYF₅ NCs can be controlled by simply tuning the reaction parameters such as reaction temperature, reaction time and the molar ratio of F⁻/Y³⁺. The detailed structure investigation reveals that the as-synthesized BaYF₅ NCs are in the cubic structure with space group Fm3¯m instead of the reported tetragonal structure. Ln³⁺ cations occupy crystal lattice positions with lower point symmetry, which may lead to high upconversion efficiency under the excitation of a 980 nm diode laser. By adjusting the dopant concentrations of Yb³⁺, Er³⁺ and Tm³⁺, intense near-infrared, blue, yellow and white upconversion emissions are readily realized, respectively. The desirable property of the ultrasmall monodisperse NCs makes it the promising material for the applications in miniaturized solid-state light sources, multicolor three-dimensional display devices and fluorescent labels for biomedicine imaging.     

Rotational spectra of isotopic species of silyl fluoride. Part II: Theoretical and semi-experimental equilibrium structure

The equilibrium structure of silyl fluoride, SiH₃F, has been reinvestigated using both theoretical and experimental data. With respect to the former, quantum-chemical calculations at the coupled-cluster level have been employed together with extrapolation to the basis set limit, consideration of higher excitations in the cluster operator, and inclusion of core correlation as well as relativistic corrections (r(Si-F) = 1.5911 Å, r(Si-H) = 1.4695 Å, and ∠FSiH = 108.30°). A semi-experimental equilibrium structure has been determined based on the available rotational constants for the various isotopic species of silyl fluoride (²⁸SiH₃F, ²⁸SiD₃F, ²⁹SiH₃F, ²⁹SiD₃F, ³⁰SiH₃F, ³⁰SiD₃F, ²⁸SiH₂DF, and ²⁸SiHD₂F) together with computed vibrational corrections to the rotational constants (r(Si-F) = 1.59048(6) Å, r(Si-H) = 1.46948(9) Å, and ∠FSiH = 108.304(9)°).     

Growth,structure and optical properties of an efficient NLO crystal-aqua maleatocopper(II)

A promising non-linear optical (NLO) crystal, aqua maleatocopper(II) (CuC₄H₂O₄·H₂O), was grown at room temperature by the controlled ionic diffusion technique. Fourier transform infrared spectrum could identify the various functional groups in the crystal. Structural analysis using single crystal XRD revealed that the compound crystallizes in the monoclinic system with space group P2₁ and unit cell parameters a = 7.7277(5) Å, b = 5.2967(3) Å, c = 7.7179(4) Å, α = γ = 109.170(5)°, β = 111.995(2)°. The thermal stability and decomposition pattern of the material were explored using thermogravimetry (TG) and differential thermal analysis (DTA). The optical band gap energy of the material was estimated as 2.2 eV from the diffuse reflectance spectroscopy. The Kurtz and Perry powder technique established the crystal to be an efficient non-linear optical (NLO) material.     

Crystal structure of the quaternary compound CuTa2InTe4 from X-ray powder diffraction

The crystal structure of the new quaternary compound CuTa₂InTe₄ was studied using X-ray powder diffraction data. The powder pattern refined by the Rietveld method indicates that this material crystallizes in the tetragonal system with space group I-4¯2m (No. 121), Z=2, and unit cell parameters a=6.1963(2) Å, c=12.4164(4) Å, c/a=2.00 and V=476.72(3) Å³. The structural and instrumental refinement of 28 parameters led to R_p=10.4%, R_wp=11.1%, R_exp=6.8% and χ²=2.7 for 96 independent reflections.     

Structural phase transitions at high-temperature in double perovskite Sr2GdRuO6

The crystal structure evolution of the Sr₂GdRuO₆ complex perovskite at high-temperature has been investigated over a wide temperature range between 298 K≤T≤1273 K. Powder X-ray diffraction measurements at room temperature and Rietveld analysis show that this compounds crystallizes in a monoclinic perovskite-type structure with P2₁/n (#14) space group and the 1:1 ordered arrangement of Ru⁵⁺ and Gd³⁺ cations over the six-coordinate M sites, with lattice parameters a=5.81032(8) Å, b=5.82341(4) Å, c=8.21939(7) Å, V=278.11(6) Å³ and angle β=90.311(2)^o. The high-temperature analysis shows that this material suffers two-phase transitions. At 373 K it adopts a monoclinic perovskite structure with I2/m space group, and lattice parameters a=5.81383(2) Å, b=5.82526(4) Å, c=8.22486(1) Å, V=278.56(2) Å³ and angle β=90.28(2)^o. Above of 773 K, it suffers a phase transition from monoclinic I2/m to tetragonal I4/m, with lattice parameters a=5.84779(1) Å, c=8.27261(1) Å, V=282.89(5) Å³ and angle β=90.02(9)^o. The high-temperature phase transition from monoclinic I2/m to tetragonal I4/m is characterized by strongly anisotropic displacements of the anions.     

Large amplitude bending motion in CsOH, studied through ab initio-based three-dimensional potential energy functions

The large-amplitude bending motion in CsOH, a ‘classical’ molecule whose microwave spectrum was first recorded in 1967, has been studied ab initio. The three-dimensional potential energy surface has been calculated at the RCCSD(T)_DK3/[QZP + g ANO-RCC (Cs, O, H)] level of theory and employed in MORBID calculations of the rotation-vibration energies and intensities. The ground electronic state is ¹Σ⁺ with the equilibrium structure r_e(Cs-O) = 2.3930 Å, r_e(O-H) = 0.9587 Å, and ∠_e(Cs-O-H) = 180.0°. The O-H moiety is bound to Cs by an ionic bond and the molecule can be described as Cs^δ+(OH)^δ-. Hence, the bending potential is shallow and gives rise to large-amplitude bending motion. The ro-vibrationally averaged structural parameters, determined as expectation values over MORBID wavefunctions, are 〈r(Cs-O)〉₀ = 2.3987 Å, 〈r(O-H)〉₀ = 0.9754 Å, and 〈∠(Cs-O-H)〉₀ = 163°. Although the averaged structure in the vibrational ground state is far from being linear, the Yamada-Winnewissi-linearity parameter for CsOH is γ₀≈-1.0, the value characteristic for a linear molecule.     

Upconversion luminescence and magnetic properties of ligand-free monodisperse lanthanide doped BaGdF5 nanocrystals

Lanthanide (Ln=Yb³⁺, Er³⁺and Tm³⁺) doped monodisperse oleate-capped BaGdF₅ nanocrystals with a mean diameter of approximately 18 nm were prepared via liquid-solid-solution method. The cell parameter of the as-prepared cubic BaGdF₅ nanocrystals is 5.884 Å, which is different from the reported 6.023 Å (JCPDS 24-0098). When excited by a 980 nm laser, these Ln³⁺ doped nanocrystals exhibit multi-color up-conversion (UC) emissions including blue, yellow and white, by precisely adjusting the dopant concentration of Yb³⁺, Er³⁺ and Tm³⁺. The oleate ligands capped on the surface of the as-synthesized products, which can be conversed from hydrophobic to hydrophilic along with certain extent of weakening of UC intensity, can be moved by the acid treatment process. The measured field dependence of magnetization (M-H curves) of the BaGdF₅ nanocrystals shows excellent paramagnetism. At room temperature, the magnetization of BaGd_0.798Yb_0.2Tm_0.002F₅ nanocrystals is 0.9165 emu/g and the magnetic mass susceptibility reaches 6.11×10⁻⁵ emu g⁻¹ Oe⁻¹ at 15 kOe. Our results indicate that these bi-functional hydrophilic Ln³⁺ doped BaGdF₅ nanocrystals have potential applications in color displays, bioseparation and optical-magnetic dual modal nanoprobes in biomedical imaging.     

Synthesis and characterization of Co7(OH)12(C2H4S2O6)(H2O)2—a single crystal structural study of a ferrimagnetic layered cobalt hydroxide

A novel layered hydrotalcite-like material, Co₇(H₂O)₂(OH)₁₂(C₂H₄S₂O₆), has been prepared hydrothermally and the structure determined using single crystal X-ray diffraction (a=6.2752(19) Å, b=8.361(3) Å, c=9.642(3) Å, α=96.613(5)°, β=98.230(5)°, γ=100.673(5)°, R1=0.0551). The structure consists of brucite-like sheets where 1/6 of the octahedral sites are replaced by two tetrahedrally coordinated Co(II) above and below the plane of the layer. Ethanedisulfonate anions occupy the space between layers and provide charge balance for the positively charged layers. The compound is ferrimagnetic, with a Curie temperature of 33 K, Curie-Weiss θ of −31 K, and a coercive field of 881 Oe at 5 K.     

Synthesis, growth, and characterization of a non-linear optical crystal-glycine lithium chloride

A new non-linear optical material, glycine lithium chloride, was synthesized and single crystals were grown by slow evaporation solution growth technique at constant temperature from its aqueous solution. Transparent and well-crystallized hexagonal prisms were obtained by controlled evaporation at a constant temperature of 45 °C. The grown crystals were characterized by X-ray diffraction methods, Fourier transforms infrared spectroscopy, and optical absorption spectrum. Single crystal X-ray diffraction analysis revealed that the crystal lattice of glycine lithium chloride is hexagonal with unit cell a = b = 7.023 Å, c = 5.478 Å, α = β = 90°, γ = 120°, V = 234 Å³. The dielectric response of the crystal with varying frequencies was studied. The second harmonic generation efficiency of the crystal was studied and is found to be larger than KDP.     

Crystal structure and compressibility of a high-pressure Ti-rich oxide, (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81, isomorphous with cubic zirconia

A Ti-rich oxide, (Ti_0.50Zr_0.26Mg_0.14Cr_0.10)_∑=1.0O_1.81, was synthesized at 8.8 GPa and 1600 °C using a multi-anvil apparatus. Its crystal structure at ambient conditions and compressibility up to 10.58 GPa were determined with single-crystal X-ray diffraction. This high-pressure phase is isomorphous with cubic zirconia (fluorite-type) with space group Fm3¯m and unit-cell parameters a=4.8830(5) Å and V=116.43(4) Å³. Like stabilized cubic zirconia, the structure of (Ti_0.50Zr_0.26Mg_0.14Cr_0.10)O_1.81 is also relaxed, with all O atoms displaced from the (, , ) position along 〈1 0 0〉 by 0.319 Å and all cations from the (0, 0, 0) position along 〈1 1 1〉 by 0.203 Å. No phase transformation was detected within the experimental pressure range. Fitting the high-pressure data (V vs. P) to a third-order Birch-Murnaghan EOS yields K₀=164(4) GPa, K′=4.3(7), and V₀=116.38(3) Å³. The bulk modulus of (Ti_0.50Zr_0.26Mg_0.14Cr_0.10)O_1.81 is significantly lower than that (202 GPa) determined experimentally for cubic TiO₂ or that (~210 GPa) estimated for cubic ZrO₂. This study demonstrates that cubic TiO₂ may also be obtained by introducing various dopants, similar to the way cubic zirconia is stabilized below 2370 °C. Furthermore, (Ti_0.50Zr_0.26Mg_0.14Cr_0.10)O_1.81 has the greatest ratio of Ti⁴⁺ content vs. vacant O²⁻ sites of all doped cubic zirconia samples reported thus far, making it a more promising candidate for the development of electrolytes in solid oxide fuel cells.     

Studies on vibrational, dielectric, mechanical and thermal properties of organic nonlinear optical co-crystal: 2,6-diaminopyridinium-4-nitrophenolate-4-nitrophenol

This article presents the vibrational, dielectric, mechanical and thermal properties of 2,6-diaminopyridine-4-nitrophenolate-4-nitrophenol co-crystals (DAP:NP) grown by slow evaporation solution growth technique. It crystallizes in orthorhombic noncentrosymmetric space group Pna2₁ with cell dimension a=10.86 Å, b=12.00 Å and c=13.53 Å; α=β=γ=90° with V=1764 Å³. Functional groups present in the molecule have been identified from FTIR study. Dielectric constant (ε_r), dielectric loss (tanδ) and ac conductivity (σ_ac) behaviors of the crystals have been studied at different temperatures. Presence of piezoelectric resonance peaks at lower frequency in dielectric measurements may increase the electro-optic coefficient of the crystals. Mechanical strength and its parameters of the grown crystals have been determined by Vickers microhardness test. TG/DTA analysis shows the melting point of the material is 150 °C and it undergoes two stages of decomposition.     

Optical,spectral and thermal properties of organic nonlinear optical single crystal: 2,3-Dimethoxy-10-oxostrychnidinium hydrogen oxalate dihydrate

The potential organic nonlinear optical single crystal of 2,3-dimethoxy-10-oxostrychnidinium hydrogen oxalate dihydrate has been grown by slow evaporation solution growth technique (SEST) using ethanol–water solution at room temperature. The powder X-ray diffraction study reveals that the crystal belongs to orthorhombic system with non-centrosymmetric space group P2₁2₁2₁ and the cell parameters are a = 7.61 Å, b = 10.73 Å, c = 29.49 Å, V = 2410.75 Å³. The functional groups of the synthesized compound have been identified by FT-Raman and FTIR analyses. Photoluminescence spectroscopy study is determined to explore its efficacy towards device fabrications. Birefringence measurement has been carried out in order to analyze the optical homogeneity of the grown crystal. The optical constants such as reflectance (R) and extinction coefficient (K) have been determined from the transmittance data. The relative second harmonic efficiency of the compound is found to be 4 times greater than that of KDP. DTA-DSC measurements indicate that the crystal is thermally stable up to 174 °C.     

Synthesis, structure and magnetic properties of the new double perovskite Ca2CrSbO6

The title double perovskite has been synthesized by solid-state reaction in air. The crystal structure has been studied from powder X-ray diffraction data. Rietveld fits to the pattern show that this compound has a monoclinic symmetry [a=5.4932(3) Å, b=5.4081(3) Å, c=7.6901(5) Å, β=90.0022(1)°, at 300 K] defined in the space group P2₁/n, where the Cr and Sb cations are almost completely ordered in the B-sublattice of the perovskite structure. Magnetic susceptibility and magnetization measurements show that this compound behaves as a Curie-Weiss paramagnet at high temperatures with μ_eff=3.53(1) μ_B and θ_P=8 K, and exhibits a robust ferromagnetic component below the ordering temperature of T_C=13 K, with a saturation magnetization of 2.36 μ_B/f.u. at 5 K. To our knowledge, this is the first example of a ferromagnetic double perovskite containing a non-magnetic element, such as Sb, occupying one half of the B positions of the perovskite structure.     

Synthesis and hydrolysis of octacalcium phosphate and its characterization by electron microscopy and X-ray diffraction

Octacalcium phosphate (OCP) powder was produced by precipitating 250 mL Ca(CH₃COO)₂ 0.04 M into 750 L of phosphate solution (5 mmol Na₂HPO₄ and 5 mmol NaH₂PO₄) at a constant temperature of 60 °C and pH 5, which resulted in a dry white powder. X-ray diffraction (XRD), transmission electron microscopy (TEM) analysis, and the electron diffraction pattern (SAED) all showed only OCP. Hydroxyapatite (HAP) was directly obtained through hydrolysis of the powder. The total transformation of OCP into HAP was registered over a period of 6 h. During the first 30 min of hydrolysis both phases coexisted. The two phases and the OCP-HAP interface were structurally analyzed through XRD and TEM. OCP parameters (calculated by the Rietveld method) are a=19.70, b=9.50, c=6.85 Å; α=90.03°, β=92.48°, γ=108.32° (triclinic P-1) with average crystal size of 13.5±0.2 nm, while HAP parameters were a=9.45, c=6.87 Å (hexagonal P6₃/m) with average crystal size of 16.9±0.2 nm.     

The crystal structure and magnetic properties of the 1-dimensional dihalide-bridged polymers dichlorobis(thiazole)cobalt(II) and dibromobis(thiazole)-cobalt(II)

The isostructural polymeric compounds Co(thiazole)₂X₂ (X=Cl (1), Br(2)) have been synthesised by the addition of thiazole to an ethanolic solution of the corresponding anhydrous cobalt halide. Powder X-ray and neutron diffraction measurements were used for structural determination. The structures were determined using powder neutron diffraction data and Rietveld techniques: (1) C2/c, a=17.806(2) Å, b=3.6806(6) Å, c=14.807(3) Å, β=94.78(1)°, V=967.1(3) ų, Z=4; (2) C2/c, a=18.079(3) Å, b=3.8138(8) Å, c=15.022(4) Å, β=92.71(1)°, V=1034.6(4) ų, Z=4. Each linear polymer chain is composed of pseudo-octahedral, high-spin Co²⁺ centres, doubly linked by halide bridges. Magnetisation measurements of 1 and 2 at 5 K between 0 and 10 kG reveals a metamagnetic transition between antiferromagnetic and ferromagnetic states. Low temperature susceptibility data have been fitted to a one-dimensional Ising model with a mean field correction and were found to be anisotropic with ferromagnetic intrachain interactions along the b-axis and weaker antiferromagnetic interchain interactions.     

Thermal variation of structure and electrical conductivity in Bi14WO24

Structure and electrical conductivity of Bi₁₄WO₂₄ as a function of temperature have been examined by X-ray and neutron powder diffraction, a.c. impedance spectroscopy and differential thermal analysis. The room temperature structure was successfully refined using a monoclinic subcell model in space group I2/m. However, additional reflections in the neutron data are consistent with a large supercell of dimensions a = 17.3780(1) Å, b = 17.3891(1) Å, c = 26.1785(2) Å and β = 90.270(1)°, as previously proposed. Transitions to tetragonal and cubic phases are observed at ca. 35 °C and 780 °C, respectively. The structure of the high temperature polymorph is confirmed as a fully disordered δ-Bi₂O₃ type phase. Analysis of the defect structure is consistent with a predominantly tetrahedral environment for tungsten, as seen at low temperatures. The conductivity behaviour is correlated with the appearance of the δ-phase at high temperatures and exhibits a value of 0.97 S cm^− 1 at 800 °C.