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1.
《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   

2.
A new low temperature modification of TaTe2 is reported (structural data at T = 150 K: C2/m (no. 12), Z = 18, a = 14.792(1) Å, b = 10.8829(9) Å, c = 9.3005(7) Å, β = 110.693(1)°). Temperature dependent single crystal X-ray diffraction, magnetic susceptibility, resistivity, specific heat capacity and differential scanning calorimetry measurements all show a phase transition at TPT  170 K. The structural change is mainly reflected by a shift of only 2/9 of the Ta atoms by 0.283 Å, which leads to clustering of the Ta atoms. The bonding patterns were derived from the Crystal Orbital Hamiltonian Population and from the Electron Localization Function based on Density Functional Theory calculations, respectively. Differences to the room temperature modification and to the hypothetical 1T-TaTe2 structure are elaborated. It is suggested, that the room temperature structure might show a dynamic type of disorder, with the X-ray structure analysis reflecting the time averaged structure.  相似文献   

3.
《Materials Research Bulletin》2006,41(8):1543-1549
Compounds with the composition Bi6(Bi1−yMy)X2O16−z, M = transition metal or Pb, X = P, V, As, display pseudo-tetragonal crystal systems. They are, however, monoclinic with space group I2 and the heavy atom positions mimic the δ-Bi2O3 structure. The title compound is monoclinic, a = 11.284(2) Å, b = 5.4259(11) Å, c = 11.112(2) Å, β = 96.25(3)°, I2, Z = 2. Least-squares refinement of single-crystal X-ray diffraction data on F2 converged to R1 = 0.050, wR2 = 0.130. The crystal is twinned by two-fold rotation about [0 1 0] and each twin consists of its inverted component forming a racemate. The structure consists of chains of edge sharing (OBi4) tetrahedra parallel to [1 0 −1]. The chains are bridged parallel to [1 0 1] by linked PO4 tetrahedra and (Mn/Bi)O6 octahedra parallel to [1 0 −1], into a three-dimensional structure. The lone-pair electrons of adjacent Bi atoms along the chain point in opposite directions along the b-axis. The Bi atoms are in distorted trigonal prismatic coordination that has one or two faces capped. The BiO bond lengths vary from 2.08(5) to 3.05(2) Å. The Mn/Bi atoms are disordered around the two-fold axis. Three oxygen atom sites contain vacancies.  相似文献   

4.
《Materials Letters》2007,61(11-12):2382-2384
A new copper thioborate, CuBS2, was synthesized at high-pressure/temperature condition of 3 GPa and 700–900 °C. The crystal structure was refined by the Rietveld analysis of the powder X-ray diffraction data. The compound crystallizes into a tetragonal unit cell (a = 0.5044(1) nm, c = 0.8947(2) nm, space group: I-42d), isostructural with CuMS2 chalcopyrite compounds (M: Al, Ga, and In). The compound is the first representative of the chalcopyrite-type family consisting of BS4-tetrahedra. From the UV–Vis diffuse reflectance spectrum, the optical band gap of CuBS2 was estimated to be Eg = 3.61 eV.  相似文献   

5.
《Optical Materials》2010,32(12):1831-1834
A large family of Sn2yPb2(1−y)P2S6xSe6(1−x) semiconductor-ferroelectric crystals were obtained by the Bridgman technique. The photoluminescence properties of the Sn2yPb2(1−y)P2S6xSe6(1−x) family crystals strongly depend on their chemical composition, excitation energy and temperature. The influence of the Pb  Sn and S  Se isovalent substitutions on the luminescence properties of a crystal with the Sn2P2Se6 basic composition was investigated. A broad emission band observed in the Sn2P2Se6 crystal with a maximum roughly at 600 nm (at T = 8.6 K) was assigned to a band-to-band electron-hole recombination, whereas broad emission bands, peaked near 785 nm (at T = 8.6 K) and 1025 nm (at T = 44 K) were assigned to an electron-hole recombination from defect levels localised within the bandgap. Possible types of recombination defect centres and specific mechanisms of luminescence in the Sn2P2Se6 semiconductor-ferroelectric crystals were considered and discussed on the basis of the obtained results and the referenced data.  相似文献   

6.
《Materials Letters》2005,59(29-30):3861-3865
A coordinated iron phosphate, Fe(bipy)(HPO4)(H2PO4) (I), has been hydrothermally synthesized and characterized by elemental analysis, thermogravimetric analysis, and single crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/n (No. 14), with cell parameters M = 405.00, a = 10.904(4) Å, b = 6.4210(2) Å, c = 19.294(9) Å, β = 101.24(4) Å3, V = 1324.9(9) Å3, Z = 4, R1 [I > 2((I)) = 0.0357, wR2 [I > 2((I)) = 0.0717. This compound displays a new structure of ladder-like chains, in which each one-dimensional chain is constituted by the distorted octahedral units of Fe3+ bridged through PO4 tetrahedra. The bipy ligands in the compound bind in a bidentate fashion to the iron atoms and the ladder-like structure of the compound extends into a three-dimensional supramolecular array via π–π stacking interactions of bipy ligands and strong hydrogen bonding between the chains. Mössbauer spectroscopy shows the presence of Fe3+ in the octahedral coordination. Magnetic susceptibility measurements show that this material may model as anti-ferromagnetic.  相似文献   

7.
Bulk crystals of Ba2Na3(B3O6)2F (BNBF) have been successfully grown by top-seeded solution growth (TSSG) technique. Its transmittance spectra show a wide transparency range from 186 nm to 3000 nm. The refractive indices in 13 wavelengths were measured with high accuracy and the Sellmeier equations were obtained, which demonstrated that the title crystal displayed a birefringence (Δn = 0.1030 at 588 nm) comparable to that of the commercial birefringent crystal α-BBO (the high temperature form of BaB2O4). A prototype Glan-Taylor polarizer made of BNBF prisms was fabricated, which showed high transparency and large optical extinction ratio similar to the commercial polarizer made of α-BBO. In addition, BNBF crystal is less moisture sensitive than that of α-BBO, thus BNBF can be a potential new birefringent crystal.  相似文献   

8.
《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   

9.
Spinel (MgAl2O4) crystals doped with 1.0% Mn have been grown by floating zone (FZ) technique with various Mg compositions, x = MgO/Al2O3, from 0.2 to 1.0. Compositional variations of photoluminescence are evaluated for a fluorescence thermometer application using crystals grown. Strong photoluminescence (PL) peak is observed at λ from 512 to 520 nm from the crystals grown from compositions, x, from 0.3 to 1.0. Peak wavelength of PL increases linearly from 512 to 520 nm with x. Weak PL peaking at λ = 750 nm is also observed from the specimens. Compositional variations of PL are considered to be due to the variation of crystal field surrounding the Mn2+ ions. The variation of crystal field strength agrees with the compositional variation of lattice constant.  相似文献   

10.
《Materials Research Bulletin》2013,48(4):1598-1605
Fluorine insertion into the oxygen defect superstructure manganite Sr2MnO3.5+x has been shown by transmission electron microscopy (TEM) to result in two levels of fluorination. In the higher fluorine content sections, the fluorine anions displace oxygen anions from their apical positions into the equatorial vacancies, thus destroying the superstructure and reverting to a K2NiF4-type structure (a = 3.8210(1) Å and c = 12.686(1) Å). Conversely, lower fluorine content sections retain the Sr2MnO3.5+x defect superstructure, crystallising in the P21/c space group. Fluorine intercalation into the reduced double-layer manganite Sr3Mn2O6 occurs in a step-wise fashion according to the general formula Sr3Mn2O6Fy with y = 1, 2, and 3. It is proposed that the y = 1 phase (a = 3.815(1) Å, c = 20.29(2) Å) is produced by the filling of all the equatorial oxygen vacancies by fluorine atoms whilst the y = 2 phase (a = 3.8222(2) Å, c = 21.2435(3) Å) has a random distribution of fluorine anions throughout both interstitial rocksalt and equatorial sites. Neutron powder diffraction data suggest that the fully fluorinated y = 3 phase (a = 3.8157(6) Å, c = 23.666(4) Å) corresponds to the complete occupation of all the equatorial oxygen vacancies and the interstitial sites by intercalated fluorine.  相似文献   

11.
《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   

12.
《Materials Research Bulletin》2006,41(5):1001-1007
The crystal structure of the 1222-type ruthenocuprate RuSr2Nd0.9Y0.2Ce0.9Cu2O10 has been studied by time-of-flight neutron diffraction at temperatures 100–160 K and pressures up to 5 GPa. The structure has tetragonal I4/mmm symmetry throughout (e.g. a = 3.8104(2) Å and c = 28.125(3) Å at 160 K and 5.1 GPa) with no significant distortions observed at the 140 K Ru spin ordering transition. The strongly bonded Cu–O and Ru–O network leads to a bulk modulus of 145 GPa which is high for layered cuprates, with a low anisotropy in the cell compressibility (kc/ka = 1.32). The Cu–O–Cu buckling angle and the tilting of the CuO5 square pyramids decreases with pressure, but the in-plane rotation of the RuO6 octahedra increases.  相似文献   

13.
《Materials Letters》2007,61(19-20):4152-4155
SnO2 nanowires were fabricated using a simple and economical method of rapid heating SnO2 and graphite powders at 850 °C in a flow of high-purity N2 as carrier gas. Research by using X-ray diffraction (XRD) indicates that SnO2 nanowires are primitive tetragonal in structure with the lattice constant a = b = 0.443 nm and c = 0.372 nm. Observations by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that SnO2 is of nanowire structure. The selected area electron diffraction (SAED) shows that the nanowires are perfect single crystal structure. The Fourier transform infrared (FT-IR) exhibits the difference of nanostructure materials and general materials. The field emission (FE) properties had also been studied.  相似文献   

14.
《Materials Research Bulletin》2006,41(8):1550-1557
Two new three-dimensional chromium(III) dicarboxylate, MIL-105 or CrIII(OH)·{O2C-C6(CH3)4-CO2nH2O, have been obtained under hydrothermal conditions, and their structures solved using X-ray powder diffraction data. Both solids are structural analogs of the known Cr benzenedicarboxylate compound (MIL-53). Both contain trans corner-sharing CrO4(OH)2 octahedral chains connected by tetramethylterephthalate di-anions. Each chain is linked by the ligands to four other chains to form a three-dimensional framework with an array of 1D pores channels. The pores of the high temperature form of the solid, MIL-105ht, are empty. However, MIL-105ht re-hydrates at room temperature to finally give MIL-105lt with pores channels filled with free water molecules (lt: low temperature form; ht: high temperature form). The thermal behaviour of the two solids has been investigated using TGA. Crystal data for MIL-105ht: monoclinic space group C2/c with a = 19.653(1) Å, b = 9.984(1) Å, c = 6.970(1) Å, β = 110.67(1)° and Z = 4. Crystal data for MIL-105lt: orthorhombic space group Pnam with a = 17.892(1) Å, b = 11.165(1) Å, c = 6.916(1) Å and Z = 4.  相似文献   

15.
It has been established that M(H2PO4)2·2H2O (M = Mn, Co, Ni) are paramagnetics between 173 and 353 K with weak antiferromagnetic exchange interaction between the metal ions. In situ magnetic measurements during the thermal decomposition of the salts show that the oxidation state and the octahedral coordination of M2+ are preserved. From the data obtained it could be supposed that in M(H2PO4)2·2H2O (M = Co, Ni) this process is topotactic with no long-range diffusion transport. In Mn(H2PO4)2·2H2O, the formation of the large variety of intermediate products probably requires more drastic rearrangement and diffusion of the manganese ions during the complex transformations, which reflect on both the value and the sign of the θ constants. M2P4O12 (M = Mn, Co, Ni), which are the final decomposition products of the corresponding dihydrogen phosphates are paramagnetics in the temperature range of 295–573 K with antiferomagnetic interactions between the metal ions. The lattice parameters of Ni(H2PO4)2·2H2O have been calculated. It crystallizes in the monoclinic system with a = 7.228(1) Å; b = 9.778(1) Å; c = 5.306(1) Å; β = 94.50(1)°, SG P21/n with Z = 2.  相似文献   

16.
《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   

17.
Two metal–organic framework compounds, [Zn3(1,4-BDC)3(Py)2]·2(1,4-dioxane) (MOF-CJ6) and [Cd3(bpdc)3(H2O)2] (MOF-CJ7), have been solvothermally synthesized and characterized by single crystal X-ray diffraction, X-ray powder diffraction, ICP, IR and photoluminescence spectroscopy analyses, respectively. MOF-CJ6 crystallizes in monoclinic, space group P2(1)/n (no. 14) with a = 14.6886(14) Å, b = 9.6194(6) Å, c = 15.9161(16) Å and β = 105.687(6)°. Its framework can be described as a 2-D 36 tessellated net based on the assembly of trimeric Zn3(CO2)6 clusters and 1,4-benzenedicarboxylates ditopic links. The 2-D nets can be further linked into a novel 3-D supramolecular hexagonal lattice (hex) network through π–π packing interaction. MOF-CJ7 crystallizes in trigonal, space group R-3 (no. 148) with a = 14.1129(8) Å, b = 14.1129(8) Å, c = 20.1168(13) Å and γ = 120°. MOF-CJ7 exhibits analogous framework topology with that of MOF-CJ6, consisting of trimeric Cd3(CO2)6 clusters and 4,4′-biphenyldicarboxylate links.  相似文献   

18.
《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   

19.
RbCaGd(PO4)2 doped with Ce3+, Mn2+ was synthesized by the sol-gel method. The crystal structure and crystallographic location of Ce3+ in RbCaGd(PO4)2 were identified by Rietveld refinement. Powder X-ray diffraction (XRD) revealed that the structure of RbCaGd(PO4)2:Ce3+ compounds is hexagonal structure which is similar to that of hexagonal LnPO4 with the lattice constant of a = b = 7.005(57) Å, c = 6.352(05) Å, and V (cell volume) = 269.980 Å3. The photoluminescence behavior and emission mechanism were studied systematically by doping activators in the RbCaGd(PO4)2 host. The Mn2+ incorporated RbCaGd(PO4)2:Ce3+, Mn2+ compounds exhibited blue emission from the parity- and spin-allowed f-d transition of Ce3+ and orange-to-red emission from the forbidden 4T1  6A1 transition of Mn2+. The emission chromaticity coordinates of RbCaGd(PO4)2:0.10Ce3+, xMn2+ (x = 0.16, 0.25) are close to the white region due to an energy transfer process and the energy transfer mechanism from Ce3+ to Mn2+ in the RbCaGd(PO4)2 host was dominated by dipole-dipole interactions.  相似文献   

20.
《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   

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