Ferroelectric properties and Raman spectroscopy of the [(C4H9)4N]3Bi2Cl9 compound.

The exploration of ferroelectric hybrid materials is highly appealing due to their great technological significance. They have the potential to conserve power and amazing applications in information technology. In line with this, we herein report the development of a [(C4H9)4N]3Bi2Cl9 tetra-alkyl hybrid compound that exhibits ferroelectric properties. The phase purity was confirmed by Rietveld refinement of the X-ray powder diffraction pattern. It crystallizes, at room temperature, in the monoclinic system with the P21/n space group. The outcome of temperature dependence of the dielectric constant proved that this compound is ferroelectric below approximately 238 K. The dielectric constants have been fitted using the modified Curie-Weiss law and the estimated γ values are close to 1. This confirms classical ferroelectric behavior. Raman spectroscopy is efficiently utilized to manifest the origin of the ferroelectricity, which is ascribed to the dynamic motion of cations as well as distortion of the anions. Moreover, the analysis of the wavenumbers and the half-width for δs(Cl-Bi-Cl) and ω(CH2) modes, based on the order-disorder model, allowed us to obtain the thermal coefficient and activation energy near the para-ferroelectric phase transition.

Using Raman spectroscopy to understand the origin of the phase transitions observed in [(C3H7)4N]2Zn2Cl6 compound.

Phase transitions of the centrosymmetric compound, [(C3H7)4N]2Zn2Cl6, were studied by differential scanning calorimetry (DSC), X-ray diffraction, Raman spectroscopy and dielectric measurements. Two reversible order-disorder and displacive phase transitions are observed at T1=327K and T2=347K with 3K and 4K hysteresis respectively, indicating a first order character. The evolution of Raman line shifts, "ν", and the half-width, "Δν", versus temperature show some singularities associated with the transitions, suggesting that they are governed by the reorientational and the displacement of the organic part. Besides the results of the dielectric permittivity study confirms the conclusion drawn from the calorimetric and Raman measurements that the phase transition located in the vicinity of the temperature of the dielectric proprieties is characterized by change of dynamical state of cation.

Synthesis, structural characterization and dielectric properties of (C6H9N2)2(Hg0.75Cd0.25)Cl4 compound.

The present paper undertakes the study of a title compound whose structure is (C6H9N2)2(Hg0.75Cd0.25)Cl4. The centrosymmetric compound crystallizes in the triclinic space group P-1, with a=7.580(7) Å; b=8.572(8) Å; c=15.433(13) Å; α=84.49(5)°; ß=89.13(5)°; γ=68.53(5)° and Z=2. The crystal structure was solved and refined to R (int)=0.0212 using 7932 independent reflections. The atomic arrangement shows an alternation of organic and inorganic layers. Between layers, the cohesion is performed via N-H⋯Cl hydrogen bonding, yet in the organic sheets, cations are further connected to classical π-π stacking. The Infrared and Raman spectra of this compound reported from 400 to 4000 cm(-1) confirmed the presence of the principal bands assigned to the internal modes of organic cation. Solid-state (13)C and (111)Cd CP-MAS-NMR spectra are reported. The dielectric study of this compound has been measured, in order to determine the σ(d.c) conductivity which is thermally activated with activation energy about 1.5 eV.

Polarized Raman study of [N(C3H7)4]2Cd2Cl6 single crystal.

Chemical preparation, mid-infrared and Raman spectra of [N(C(3)H(7))(4)](2)Cd(2)Cl(6) are presented. Polarized Raman spectra of oriented single crystals have been recorded in the range 7-3900 cm(-1) under various polarization configurations with regard to the symmetry and the numbers of several band modes observed in the Raman and infrared spectra. The obtained results are consistent with the theoretical predictions based on the infrared and Raman selection rules.

Vibrational study of [(CH3)4N]2Cu0.5Zn0.5Cl4.

[(CH3)4N]2Zn0.5Cu0.5Cl4 shows an orthorhombic system at ambient temperature with P2(1)nb space group. At room temperature, the crystal consists of three sublattices constituted by MCl4 (M=Cu and Zn) and two tetramethylammoniums N1(CH3)4 and N2(CH3)4, which give rise to a total of 372 vibrational modes that transform according to the four irreductible representations of the C2v point group in the following way: Gamma(vib)=93(A1+A2+B1+B2). The infrared and Raman spectra of polycrystalline samples have been investigated at room temperature. The assignment of the observed bands is discussed.

Correlation between 31P chemical shift tensor and local structure in lithium cyclohexaphosphates Li6P6O18 x 3H2O and Li6P6O18.

To understand the surprising behavior between the variations of the P'-P-P" angles and the correlated variations of the O'-P-O" ones, two lithium cyclohexaphosphate compounds Li6P6O18 x 3H2O and Li6P6O18 are studied by solid state nuclear magnetic resonance (NMR) spectroscopy. The two compounds exhibit the same [P6O18]6- ring anions but with 3m or 1 internal symmetry, respectively. Such symmetries induce local distortions that are exhibited by NMR spectroscopy. One-dimensional (1D) NMR gives information on structural sites of 7Li and 31P ions and the crystallographic non-equivalencies are observed. Nevertheless, in the anhydrous compound, X-ray diffraction and NMR results do not completely agree and some discrepancy exists between the number of sites observed with the first technique and the number of lines exhibited in the NMR spectra either for 7Li or 31P nuclei. This problem is elucidated by using 2D double quantum NMR spectroscopy coupled with theoretical considerations. We find that the 31P chemical shift tensor is dependent on the deviations of the O-P-O angles from those in the regular tetrahedron. Within the same empirical model, we suggest that the surprising behavior between the variations of the P'-P-P" and the ones of the O'-P-O" is related to the overall charge on the PO4 group. We also find the positions of the isotropic lines for 7Li essentially depend on the site co-ordination of this nuclei.