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1.
《Materials Research Bulletin》2006,41(10):1835-1844
(C2N2H10)[FexV1−x(HPO3)F3] (x = 0.44, 0.72) have been synthesized using mild solvothermal conditions under autogenous pressure and the ethylenediamine molecule as templating agent. The crystal structures have been determined from X-ray single-crystal diffraction data. The compounds crystallize in the orthorhombic P212121 space group with Z = 4 and unit-cell parameters a = 12.8494(9), b = 9.5430(6), c = 6.4372(5) Å, and a = 12.8578(1), b = 9.5342(1), c = 6.4370(7) Å for (C2N2H10)[Fe0.44V0.56(HPO3)F3] and (C2N2H10)[Fe0.72V0.28(HPO3)F3], (1) and (2), respectively. These isostructural compounds exhibit a monodimensional crystal structure formed by pillared double anionic chains with the formula [M(HPO3)F3]2−, extended along the [0 0 1] direction. These doubled ionic chains are the result of the linking of two simple chains in which there are alternating octahedral [MO3F3] and tetrahedral groups [HPO3]. The ethylendiammonium cations are placed in the space delimited by three different chains. The metallic ions are interconnected by the pseudo-pyramidal (HPO3)2− phosphite oxoanions, adopting a slightly distorted octahedral geometry. The IR spectra show bands corresponding to the phosphite oxoanion and the ethylendiamonium cation at 2400 and 1600 cm−1, respectively. The thermogravimetric analyses show that these phases are stable up to ca. 280 °C, at higher temperatures, the decomposition of the crystal structure begins by calcination of the organic cation and the elimination of the fluoride anions. The diffuse reflectance spectra show bands of the V3+ ion (d2) in octahedral symmetry. The values of the Dq (1540, 1540 cm−1), and Racah parameters, B (560, 535 cm−1) and C (3055, 3140 cm−1) for (1) and (2), respectively, correspond with those usually found for octahedrically coordinated V(III) compounds. Magnetic measurements, performed on a powered sample from 5.0 to 300 K at 1000 G, in the ZFC and FC modes, indicate the existence of antiferromagnetic interactions.  相似文献   

2.
《Materials Research Bulletin》2006,41(10):1917-1924
Chemical preparation, X-ray single-crystal, thermal behavior, and IR spectroscopy investigations are given for a new organic cation dihydrogenomonophosphate (C6H8N3O)2(H2PO4)2 (denoted IAHP) in the solid state. This compound crystallizes in the orthorhombic space group P212121. The unit cell dimensions are: a = 7.422(3) Å, b = 12.568(5) Å, c = 20.059(8) Å with V = 1871.1(13) Å3 and Z = 4. The structure has been solved using direct method and refined to a reliability R factor of 0.029. The atomic arrangement can be described as inorganic layers of H2PO4 anions between which are located the organic groups (C6H8N3O)+ through multiple hydrogen bonds.  相似文献   

3.
《Materials Research Bulletin》2006,41(7):1287-1294
Chemical preparation, crystal structure and NMR spectroscopy of a new organic cation p-phenylenediammonium monophosphate [p-NH3C6H4NH3][H2PO4]2 are presented. This new compound crystallizes in the orthorhombic system, with the space group Pnma and the following parameters: a = 7.970 (2) Å; b = 22.770 (7) Å; c = 7.000 (7) Å, V = 1270.3 (11) Å3, Z = 4 and Dx = 1.590 g cm−3. The crystal structure has been determined and refined to R = 0.043 and R(w) = 0.057 using 2623 independent reflections. The structural arrangement can be described as inorganic layers of (H8P4O16)4− units, parallel to (a, c) planes. The organic groups (p-H3NC6H4NH3)2+are anchored between the phosphoric layers to form a three-dimensional infinite network. This compound is also investigated by IR and solid-state 1H, 13C and 31P MAS NMR spectroscopies. The ab initio method is used in the calculation of chemical shifts.  相似文献   

4.
《Materials Research Bulletin》2006,41(7):1337-1344
The new phases α-NaSbP2S6 and β-NaSbP2S6 were synthesized by ceramic and reactive flux methods at 773 K. The structures of α-NaSbP2S6 and β-NaSbP2S6 were determined by the single-crystal X-ray diffraction technique. α-NaSbP2S6 crystallizes in the monoclinic space group P21/c with a = 11.231(2) Å, b = 7.2807(15) Å, c = 11.640(2) Å, β = 108.99(3)°, V = 900.0(3) Å3 and z = 4. β-NaSbP2S6 crystallizes in the monoclinic space group P21 with a = 6.6167(13) Å, b = 7.3993(15) Å, c = 9.895(2) Å, β = 92.12(3) °, V = 484.10(17) Å3 and z = 2.The α- and β-phases of NaSbP2S6 are closely related, the main difference lies in the stacking of the [Sb[P2S6]]nn layers. The structure of α-NaSbP2S6 consists of two condensed layers (MPS3 type) to give an ABAB… sequence with Na+ cations located in the interlayer space. The packing of β-NaSbP2S6 is formed by monolayers of [Sb[P2S6]]nn stacked in an AA… fashion separated by a layer of Na+ cations. Both phases are derivates of the M1+M3+P2Q6 family.The optical band gaps of α-NaSbP2S6 and β-NaSbP2S6 were determined by UV–vis diffuse reflectance measurements to be 2.17 and 2.25 eV, respectively.  相似文献   

5.
The crystal structures of [A0.92(NH4)0.08]2TeCl4Br2 with A = Cs, Rb have been determined using X-ray powder diffraction techniques. The two compounds crystallize in the tetragonal space group P4/mnc, with the unit cell parameters: a = 7.452(1) Å, c = 10.544(3) Å, Z = 2 and a = 7.315(2) Å, c = 10.354(4) Å, Z = 2 in the presence of Cs and Rb, respectively. These two compounds have an antifluorite-type arrangement of NH4+/Rb+/Cs+ and octahedral TeCl4Br22? anions. The stability of these structure is by ionic and hydrogen bonding contacts: A?Cl, A?Br and N–H?Cl, N–H?Br. The different vibrational modes of these powders were analysed by FTIR and Raman spectroscopic studies. A DTA/TGA experiment reveals one endothermic peak at 780 K implicating the decomposition of the sample. At low temperature, one endothermic peak in thermal behavior is detected at around 213 K by DSC experiment. This transition was confirmed by dielectric measurements.  相似文献   

6.
《Materials Research Bulletin》2006,41(11):2168-2180
The (C2N2H10)0.5[FexV1−x(HPO3)2] (x = 0.26, 0.52 0.74) compounds have been obtained by mild solvothermal conditions in the form of micro-crystalline powder with brown color. The crystal structures were refined by X-ray powder diffraction data using the Rietveld method. The compounds crystallize in the monoclinic system, space group P2/c with the unit-cell parameters, a = 9.262(5) Å, b = 8.823(5) Å, c = 9.714(6) Å, β = 120.84(3)°; a = 9.245(1) Å, b = 8.823(1) Å, c = 9.698(1)Å, β = 120.80(1)° and, a = 9.254(4)Å, b = 8.822(4)Å, c = 9.702(4)Å, β = 120.73(3)° for (C2N2H10)0.5[Fe0.26V0.74 (HPO3)2] (1), (C2N2H10)0.5[Fe0.52V0.48(HPO3)2] (2), and (C2N2H10)0.5[Fe0.74V0.26(HPO3)2] (3). The compounds show an open crystalline structure with three-dimensional character, whose formula for the anionic inorganic skeleton is [M(HPO3)2]2−. The inorganic framework is formed by [MO6] octahedra inter-connected by phosphite groups. The structure of the compounds exhibits channels extended along the [1 0 0] and [0 0 1] directions and the ethylendiammonium cations are located inside these channels, linked through hydrogen bonds and ionic interactions. The infrared spectra show the bands corresponding to the stretching (P–H) vibration of the phosphite group and the band corresponding to the deformation mode of the ethylendiammonium cation, δ(NH3+). The thermal and thermodiffractometric behavior show that the compounds are stable up to approximately 300 °C, at higher temperatures the decomposition of the crystal structure by calcination of the organic cation starts. The diffuse reflectance spectra show bands of the V3+ ion (d2), and a band of the Fe3+ ion (d5), in a slightly distorted octahedral symmetry. The values of the Dq and Racah parameters (B and C) have been calculated for the V(III) cation. Magnetic measurements were performed on a powdered sample from 5 to 300 K at magnetic fields 1000, 500 and 100 G, in the ZFC and FC modes. At the magnetic field of 1000 G antiferromagnetic interactions were observed, but at 100 G have been detected higher values of the χm in the FC mode than those observed in the ZFC one, indicating the existence of a dominant ferromagnetic component at low temperature. The magnetization measurements show hystheresis loops at 5 K, with values of the remanent magnetization and coercive field of 1.91 emu/mol and 23 Gauss for (1), 25 emu/mol and 300 Gauss for (2), and 3 emu/mol and 50 Gauss for the compound (3).  相似文献   

7.
A new quaternary alkali metal, rare earth thiophosphate was synthesized by the ceramic method and characterized by single crystal X-ray diffraction: K2SmP2S7 crystallizes in the monoclinic space group C2 (no. 5) with the unit cell parameters a = 22.746(5) Å, b = 6.7362(13) Å, c = 8.9004(18) Å, β = 99.68(3)°, V = 1344.3(5) Å3 and Z = 2. The phase K2SmP2S7 can be better described as K4Sm2[PS4]2[P2S6] because it contains in the crystal structure both discrete anions [PS4]3? and [P2S6]4?. The crystal structure consists of infinite chains of 1[SmPS4] that are linked together through the ethane-like [P2S6]4? anions to form two-dimensional layers. The packing of K2SmP2S7 is formed by layers of 2[Sm2[PS4]2[P2S6]]4? separated by K+ cations. K2SmP2S7 was characterized by Raman and Fourier transform infrared (FTIR) spectroscopy and SEM-EDX microprobe analyses. The optical band gap of K2SmP2S7 was determined by UV–vis diffuse reflectance measurements to be 2.59 eV.  相似文献   

8.
《Optical Materials》2008,30(12):1741-1745
Single crystal of Yb:GdYAl3(BO3)4(Yb:GdYAB) has been grown by the flux method. The structure of Yb:GdYAB crystal has been determined by X-ray diffraction analysis. The experiment show that the crystal has the same structure as that of YAl3(BO3)4 crystal and its unit cell constants have been measured to be a = 9.30146 Å, c = 7.24164 Å, Vol = 542.59 Å3. The absorption and fluorescence spectrum of Yb:GdYAl3(BO3)4 crystal have also been measured at room temperature. In the absorption spectra, there are two absorption bands at 938 nm and 974 nm, respectively, which is suitable for InGaAs diode laser pumping. In the fluorescence spectra, there are two fluorescence peaks at 992 and 1040 nm. The thermal properties of Yb:GdYAl3(BO3)4 crystal have been studied for the first time. The thermal expansion coefficient along c-axis is almost 5.4 times larger than that along a-axis. The specific heat of the crystal has been measured to be 0.77 J/g °C at room temperature. The calculated thermal conductivity is 5.26 Wm−1 K−1 along a-direction.  相似文献   

9.
The title compound, morpholin-4-ium p-aminobenzoate (MPABA)(C4H10NO+,C7H6NO2?), has been synthesized for the first time by the addition of morpholine with 4-aminobenzoic acid in equi-molar ratio and good quality single crystals have been grown by solution growth technique using methanol as a solvent. The molecular structure of the compound was solved and refined by Direct Methods using SHELXS97 and full-matrix least-squares technique using SHELXL97, respectively. MPABA crystallizes in a monoclinic system with unit cell parameters, a = 5.948(5) Å, b = 18.033(4) Å, c = 10.577(5) Å, β = 90.40(1)° and non-centrosymmetric space group Cc. The experimentally measured density and chemical compositions were found to be in good agreement with the theoretical values. The phases and functional groups of MPABA have been identified and confirmed through powder X-ray diffraction and Fourier transform infrared (FTIR) studies, respectively. The thermal stability and decomposition details were studied through TG/DTA thermograms. The UV–visible transmission spectra were recorded for the grown crystal and its NLO characteristic was explored by powder second harmonic generation (SHG) studies.  相似文献   

10.
Polycrystalline samples of BaV13O18 and SrV13O18 were prepared by solid-state reaction of BaCO3, SrCO3, V2O5 and V at 1773–2073 K in flowing Ar. The crystal structures of BaV13O18 (R-3, ah=12.6293(10) Å, ch=7.0121(4) Å) and SrV13O18 (ah=12.5491(7) Å, ch=6.9878(3) Å) were refined by the Rietveld method using X-ray diffraction data. BaV13O18 exhibited semiconducting behavior with electrical resistivity from 5.8×10−3 to 2.7×10−3 Ω cm at 100–300 K. Electrical resistivity of SrV13O18 ranged from 1.5×10−3 to 1.8×10−3 Ω cm, and it increased slightly up to around 250 K and decreased above 250 K with increasing temperature. Negative Seebeck coefficients of both compounds at 100–300 K indicated that electron was the dominant carrier. BaV13O18 and SrV13O18 showed paramagnetism with the effective magnetic moment of 0.11μB and 0.15μB, respectively, at 10–100 K.  相似文献   

11.
《Materials Research Bulletin》2004,39(7-8):1113-1121
The aim of encapsulation of 2,3-dimethylanilinium cation in (H2XO4)n polymeric anion chains is to build acentric frameworks that are efficient for non-linear optical (NLO) applications. The synthesis and structures of two new inorganic–organic NLO crystals with general formula (2,3-(CH3)2C6H3NH3)H2XO4 (X=P, As) are reported. The magnitude of their second harmonic generations (SHG) responses was found to be between the KDP and urea. They crystallize with monoclinic unit-cells and are isotopic. We have determined the structure of phosphoric salt. The following unit-cell parameters were found: a=8.866(3) Å, b=5.909(6) Å, c=10.644(5) Å, β=112.44(1)°, V=515.5(5) Å3 and DX=1.412 g cm−3. The space group is P21 with Z=2. The structure was refined with R=0.041 (Rw=0.057) for 1652 reflections with I≥3σ(I). It exhibits infinite (H2PO4)nn chains. The organic groups (2,3-(CH3)2C6H3NH3)+ are anchored between adjacent polyanions through multiple hydrogen bonds. Chemical preparation, crystal structure, calorimetric and spectroscopic investigation are described.  相似文献   

12.
The crystal structure of the ordered fluorite, Pr3RuO7, was refined from powder neutron diffraction data in Cmcm. An interesting structural feature is the presence of relatively well separated zig-zag chains of corner sharing RuO6 octahedra, Ru–Ru interchain distance 6.61 Å vs. Ru–Ru intrachain distance of 3.76 Å. Magnetic susceptibility data show a Curie–Weiss behavior for T>225 K with C=5.96(4) emu K mol−1 and θc=+11(2) K. In an attempt to separate the contributions of Pr(3+) and Ru(5+), the properties of isostructural Pr3TaO7 were also measured, yielding C=4.63(3) emu K mol−1. Thus, the contribution of Ru(5+), 4d3, S=3/2, to the measured Curie constant is estimated to be 1.33 emu K mol−1, not far from the spin-only value of 1.87 emu K mol−1. This supports the view that the Ru 4d electrons are localized and magnetic, not itinerant. A susceptibility maximum at about 50 K is attributed to long-range magnetic order and this is substantiated by neutron diffraction data. There is little evidence for one-dimensional antiferromagnetic correlations in this material but behavior characteristic of short-range ferromagnetic correlations attributed to Pr–Ru exchange interactions are found in the temperature range 50–200 K, consistent with the positive θc.  相似文献   

13.
《Materials Letters》2007,61(14-15):3208-3210
We report here for the first time the temperature dependence of the electrical resistivity and heat capacity of nano-crystalline MgTiO3 geikielite of up to 1000 K. The temperature dependence of heat capacity of nano-crystalline geikielite expressed as Cp = 46.44(5) + 0.0502(2)T  4.56 × 106T2 + 1.423 × 103T 0.5  8.672 × 10 6T 2, where Cp = is specific heat expressed in J/mol. K and T is the temperature in K. Both the electrical resistivity and heat capacity behaviour show that the geikielite (both the natural and synthetic nano-crystalline samples) are stable and remains electrically insulating up to 1000 K.  相似文献   

14.
《Materials Research Bulletin》2006,41(11):2024-2034
The monoclinic crystal structure of (C9H15N3O2)2P2O7·H2O denoted DLTHDP [a = 14.626(1), b = 6.1990(2), c = 14.562(1) Å, β = 97.289(3)°, Z = 2, monoclinic P21, Dcal = 1.508, Dmes = 1.49 g cm−3] has been solved using direct methods and refined to a reliability factor R = 4.37% for 2079 independent reflections. The DLTHDP structure can be described by infinite polyanions [P2O7·H2O]n4n organized in chains parallel to the b-direction and located at z = 1/2, alternating with organic cations associated in ribbons spreading along the a-direction. Multiple hydrogen bonds originating from amine, hydroxyl groups and water molecules donors [NH…O(N) and O(W)H…O] connect the different components of the lattice. The IR data of DLTHDP is reported and discussed according to the theoretical group analysis and by comparison with IR results of similar compounds. The coupled thermogravimetric analysis (TGA)–differential thermal analysis (DTA) thermal study shows the departure of one water molecule, confirming the hydrated character of this compound.  相似文献   

15.
The Judd–Ofelt theory has been applied to analyze absorption spectra of Ho3+ ion in HoAl3(BO3)4 measured in spectral range 300–700 nm at room temperature. The Judd–Ofelt spectroscopic parameters have been determined as: Ω2 = 18.87 × 10−20 cm2, Ω4 = 17.04 × 10−20 cm2, Ω6 = 9.21 × 10−20 cm2. These parameters have been used to calculate radiative lifetimes and branching ratios of the luminescence manifolds. Three luminescent bands were found in the spectral range 450–700 nm ascribed to transitions from the 5F5, (5F4, 5S2) and 3K8 states to the ground state 5I8. Experimental intensities of these luminescence transitions were compared with those calculated by using Judd–Ofelt theory and the system of kinetic equations for populations of starting luminescing states. Probabilities of radiativeless transitions were evaluated from this comparison.  相似文献   

16.
A new compound, Pb3OBO3F, has been grown by the high temperature solution method from the PbO–PbF2–B2O3 system. It crystallizes in the orthorhombic system, space group Pbcm with unit-cell parameters a = 7.6313(14) Å, b = 6.5229(12) Å, c = 11.906(2) Å, Z = 4, volume = 592.66(19) Å3. The structure of the compound is solved by the direct methods and refined to R1 = 0.0528 and wR2 = 0.1400. Pb3OBO3F consists of Pb(1)O3F tetrahedra, Pb(2)O4 tetrahedra and BO3 triangles which build up the symmetrical chains extended along the c-axis. The powder X-ray diffraction pattern of the Pb3OBO3F has been measured. Functional groups presented in the sample were identified by Fourier transform infrared spectrum.  相似文献   

17.
《Materials Letters》2007,61(11-12):2499-2501
A single crystal of Tb: KLu(WO4)2 with dimensions of 40 mm × 40 mm × 18 mm has been grown by the top-seeded solution growth (TSSG) method. The color of the crystal is brown. Absorption and fluorescence spectra were measured at room temperature. The measured specific heat is a little lower than that of Yb: KLW (0.365 J/g K) at 90 °C. The measured mean linear coefficients of thermal expansion are αa = 17.1643 × 10 6 K 1, αa = 14.0896 × 10 6 K 1, αb = 8.7938 × 10 6 K 1, αc = 23.1745 × 10 6 K 1, αc = 20.2866 × 10 6 K 1. The results indicate that the crystal has a large anisotropy. The refractive index was measured.  相似文献   

18.
Eu3+ ions incorporated Li–K–Zn fluorotellurite glasses, (70  x)TeO2 + 10Li2O + 10K2O + 10ZnF2 + xEu2O3, (0  x  2 mol%) were prepared via melt quenching technique. Optical absorption from 7F0 and 7F1 levels of the Eu3+-doped glass has been studied to examine the covalent bonding characteristics, energy band gap and Judd–Ofelt intensity parameters. The emission spectra (5D0  7F0,1,2,3,4) of the glasses were used to estimate the luminescence enhancement, asymmetric environment in the vicinity of Eu3+ ions, stimulated emission cross section and branching ratios. The phonon side band mechanism of 5D2 level of the Eu3+ ions in the prepared glass was examined by considering the excitation and Raman spectra. The radiative lifetime calculated using Judd–Ofelt parameters was compared with the experimental lifetime to estimate the quantum efficiency of 5D0 level of Eu3+ ions in Li–K–Zn fluorotellurite glass.  相似文献   

19.
《Materials Letters》2006,60(9-10):1147-1150
A new A4B3O12-type cation-deficient perovskite Ba2La2TiNb2O12 was prepared by the conventional solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM). The compound crystallizes in the trigonal system with unit cell parameter a = 5.6726(3) Å, c = 27.740(2) Å, V = 773.04(9) Å3 and Z = 3. The microwave dielectric properties of the ceramic were studied using a network analyzer, and it shows a high dielectric constant of 42.70, a high quality factor with Q × f of 31,130 GHz, and a small negative τf of − 4.2 ppm °C 1.  相似文献   

20.
《Materials Research Bulletin》2004,39(4-5):677-682
Ba5LnZnTa9O30 (Ln=La, Sm) ceramics were prepared by high temperature solid-state reaction route. The samples were characterized by X-ray diffraction, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC) methods. They belong to paraelectric phase of filled tetragonal TB structure at room temperature with unit cell a=12.5909(4) Å, c=3.9622(2) Å for Ba5LaZnTa9O30; and a=12.5777(4) Å, c=3.9544(2) Å for Ba5SmZnTa9O30. At 1 MHz, Ba5LaZnTa9O30 has high dielectric constants of 89 with low dielectric loss 0.0067, and temperature coefficients of the dielectric constant (τε) −811 ppm °C−1; Ba5LaZnTa9O30 has dielectric constants of 74 with low dielectric loss 0.0035, and τε −474 ppm °C−1.  相似文献   

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