Structure and phase transitions in chloroantimonate(V) crystals: [(C2H5)3NH]SbCl6 and [(C2H5)3NH]SbCl6·1/2[(C2H5)3NH]Cl

New triethylammonium salts: [(C₂H₅)₃NH]SbCl₆ (TCA) and [(C₂H₅)₃NH]SbCl₆·1/2[(C₂H₅)₃NH]Cl (TCAT) have been synthesized. The compounds crystallise in monoclinic symmetry: space groups P2₁/n and P2₁/c, for TCA at 293 K and TCAT at 100 K, respectively. The crystal structure of [(C₂H₅)₃NH]SbCl₆ consists of discrete ionic pairs—triethylammonium cations and hexachloroantimonate anions—linked via the bifurcated N-H?Cl hydrogen bonds. The crystal structure of [(C₂H₅)₃NH]SbCl₆·1/2[(C₂H₅)₃NH]Cl is composed of three symmetrically independent triethylammonium cations, chlorine anion and two symmetrically independent hexachloroantimonate anions. TCA undergoes a structural phase transition at 336 K (on heating) into the orthorhombic C222 space group, whereas TCAT reveals a structural phase transition at 332 K. The phase transitions are of the first order type. TCA shows a ferroelastic domain structure below 336 K. Differential scanning calorimetry, dilatometric, dielectric dispersion and Raman scattering measurements have been used to study the phase transition mechanisms in these triethylammonium salts.     

On the ordering in [(C2H5)4N]2CuCl4 crystal: an X-ray study and theoretical considerations

The crystal structure [(C₂H₅)₄N]₂CuCl₄ has been determined by X-ray diffraction at 243K. The room temperature phase (phase I) belongs to the space group P4₂/nm [1] whereas the low temperature phase (phase II) is orthorhombic and belongs to the space group Pnna. The phase transition at T_c=258K is of improper ferroelastic type and it is associated with the ordering of the CuCl₄ ^2? and a partial ordering of the [(C₂H₅)₄N]⁺ ions which are disordered in the high temperature tetragonal phase. At lower temperature, there occurs another instability which could correspond to a complete ordering in the crystal.     

On the ordering in [(C2H5)4N]2CuCl4 crystal: an X-ray study and theoretical considerations

The crystal structure [(C₂H₅)₄N]₂CuCl₄ has been determined by X-ray diffraction at 243K. The room temperature phase (phase I) belongs to the space group P4₂/nm [1] whereas the low temperature phase (phase II) is orthorhombic and belongs to the space group Pnna. The phase transition at T_c=258K is of improper ferroelastic type and it is associated with the ordering of the CuCl₄ ²⁻ and a partial ordering of the [(C₂H₅)₄N]⁺ ions which are disordered in the high temperature tetragonal phase. At lower temperature, there occurs another instability which could correspond to a complete ordering in the crystal.     

Synthesis,crystal structure and electrical properties of (C5H13NCl)2 SnCl6

In this work, a novel compound Bis(2-chloropropyl-N,N-dimethyl-1-ammonium) hexachloridostannate(IV) was synthesized and characterized by; single X-ray diffraction, Hirshfeld surface analysis, differential scanning calorimetric and dielectric measurement. The crystal structure refinement at room temperature reveled that this later belongs to the monoclinic compound with P2₁/n space group with the following unit cell parameters a = 7.2894(7) Å, b = 12.9351(12) Å, c = 12.2302(13) Å and β = 93.423 (6) °. The structure consists of isolated (SnCl₆)^2? octahedral anions connected together into layers via hydrogen bonds N–H….Cl between the chlorine atoms of the anions and the hydrogen atoms of the NH groups of the [C₅H₁₃NCl]⁺ cations. Hirschfeld surface analysis has been performed to gain insight into the behavior of these interactions. The differential scanning calorimetry spectrum discloses phase transitions at 367 and 376.7 K. The electrical properties of this compound have been measured in the temperature range 300–420 K and the frequency range 209 Hz–5 MHz. The Cole–Cole (Z′ versus Z″) plots are well fitted to an equivalent circuit model. The transition phase observed in the calorimetric study is confirmed by the change as function of temperature of electrical parameter such as the conductivity of grain (σ_g) and the σ_dc.     

Investigation of the nonlinear absorption and optical limiting properties of two [Q]2[Cu(C3S5)2] compounds

The nonlinear absorption properties of two organometallic compounds, [(C₂H₅)₄N]₂[Cu(C₃S₅)₂] (DCu1) and [(C₄H₉)₄N]₂[Cu(C₃S₅)₂] (DCu2), have been investigated using an open-aperture Z-scan technique at 1064 nm with 40 ps pulse width and at 1053 nm with 18 ns pulse width. The reverse saturable absorption (RSA) which was observed in both samples with nanosecond pulse excitation was much larger than that observed with picosecond pulse excitation. The nonlinear absorption properties were analyzed theoretically by a five-level model. Optical limiting based on RSA was performed and limiting thresholds were evaluated for both samples under three conditions. DCu1 exhibited the better limiting characteristics because of its stronger RSA response.     

Phase transitions and modulated structure of the incommensurate phase in Mg[H2O]6SiF6 crystal

The temperature and angular dependences of the EPR spectra of Mg[H₂O]₆SiF₆:Mn²⁺ crystal were investigated in order to clarify the successive phase transitions and existence of the incommensurate phase. Five successive phase transitions were found to occur, and phase II was found to be incommensurately modulated. The modulated structure is caused mainly by the vibrational displacement of the Mg[H₂O]²⁺ ₆ ion along the c-axis. The soliton density of this phase is almost independent of temperature and remains equal to unity.     

Temperature evolution of the intra-ion absorption spectra of (NH2(C2H5)2)2CoCl4 crystals in the region of their phase transitions

On the basis of spectroscopic studies of (NH₂(C₂H₅)₂)₂CoCl₄ crystals, the absorption bands corresponding to the internal electronic transitions in the Co²⁺ ion were identified. The values of the crystal field and Racah parameters were calculated. The temperature evolution of the absorption spectra of (NH₂(C₂H₅)₂)₂CoCl₄ crystals reveals the anomalies of their parameters at the points of phase transitions. The corresponding changes of the absorption spectra were discussed in terms of distortion of the metal-halogen complex. The temperature dependences of the absorption spectra of (NH₂(C₂H₅)₂)₂CoCl₄ crystals confirm the presence of the thermochromic phase transitions at 255 and 330?K.     

Phase transitions in a metal–organic coordination polymer: [Zn2(C8H4O4)2(C6H12N2)] with guest molecules. Thermal effects and molecular mobility

Thermal effects of a series of [Zn₂(C₈H₄O₄)₂(C₆H₁₂N₂)] porous compound with the guest molecules located in the pores were studied using differential scanning calorimetry combined with solid-state ¹H nuclear magnetic resonance spectroscopy. The intercalation of the molecules was shown to produce various thermal anomalies and phase transitions, which were characterized and analyzed.     

Raman studies of phase transitions in ferroelectric [C2H5NH3]2ZnCl4

The present paper accounted for the synthesis, differential scanning calorimetric and vibrational spectroscopy of [C₂H₅NH₃]₂ZnCl₄grown at room temperature. Differential scanning calorimetric (DSC) disclosed five phase transitions at T₁=231 K, T₂=234 K, T₃=237 K, T₄=247 K and T₅=312 K. The temperature dependence of the dielectric constant at different temperatures proved that this compound is ferroelectric below 238 K. Raman spectra as function temperature have been used to characterize these transitions and their nature, which indicates a change of the some peak near the transitions phase. The analysis of the wavenumber and the line width based on the order–disorder model allowed to obtain information relative to the thermal coefficient and the activation energy near the transitions phase.     

UPS measurements of molecular energy level of condensed gases

There have been numerous attempts to use ultraviolet photoemission spcctroscopy (UPS) to monitor the chemical states of adsorbed gas molecules on metal surfaces. To interpret the data correctly, one has to determine the effect of photoemission on the measured energy levels of the molecule. We have measured the UPS spectra of seven gases (C₆H₆, C₅H₅N, CH₃OH, C₂H₅OH, H₂CO, H₂O, NH₃) condensed on a LN₂ cooled MoS₂ substrate at hv = 21.2 eV. The inertness of the MoS₂ substrate assures that no strong chemical bonding exists between the substrate and adsorbed molecules. For each gas, the spectrum of the condensed phase is similar to the corresponding spectrum of the gas phase except all the energy levels are shifted up by the same amount. This shift ranges from 1 to 1.65 eV for the gases studied. The energy shift is attributed to the dielectric screening of the hole produced during the optical excitation.     

Electrical properties,equivalent circuit,and dielectric relaxation studies on [(C<Subscript>3</Subscript>H<Subscript>7</Subscript>)<Subscript>4</Subscript>N]<Subscript>2</Subscript>Cd<Subscript>2</Subscript>Cl<Subscript>6</Subscript> polycrystalline

The Ac electrical conductivity and the dielectric relaxation properties of the [(C₃H₇)₄N]₂Cd₂Cl₆ polycrystalline sample have been investigated by means of impedance spectroscopy measurements over a wide range of frequencies and temperatures, 209 Hz–5 MHz and 361–418 K, respectively. The purpose is to make a difference between the electrical and dielectric properties of the polycrystalline sample and single crystal. Besides, a detailed analysis of the impedance spectrum suggests that the electrical properties of the material are strongly temperature-dependent. Plots of (Z" versus Z') are well fitted to an equivalent circuit model consisting of a series combination of grains and grains boundary elements. Moreover, the temperature dependence of the electrical conductivity in the different phases follows the Arrhenius law and the frequency dependence of σ (ω) follows the Jonscher’s universal dynamic law. Furthermore, the modulus plots can be characterized by full width at half height or in terms of a nonexperiential decay function φ(t) = exp(t/t)^β. Finally, the imaginary part of the permittivity constant is analyzed with the Cole–Cole formalism.     

Further examples of 19e− sandwiches of Fe(I) studied by Mössbauer spectroscopy: Per-ethylated benzene complexes

The organometallic complexes C₅H₅ Fe(I) C₆(C₂H₅)₆ and C₅(CH₃)₅ Fe(I)C₆ H(C₂H₅)₅ have been studied by Mössbauer spectroscopy. Hyperfine data are typical for 19e^? systems with one electron on the e ₁ ^* orbital. The thermal variation of the quadrupole splittings indicates vibronic reduction of the spin-orbit constant, in agreement with previous analyses of similar 19e^? systems. The quadrupole splitting and recoil-free fraction data give evidence for phase transitions, which are discussed with respect to cooperative Jahn-Teller distortion and hindered rotations of the ethyl groups.     

From pirazoloquinolines to annulated azulene dyes: UV–VIS spectroscopy and quantum chemical study

Paper reports UV–Vis absorption and photoluminescence spectra of 6-R derivatives (R=CH₃, O–CH₃, C(C₆H₅)₃, C₆H₅–N–C₁₀H₇) of 4-(2-chlorophenyl)-1,3-diphenyl-1H-pyrazolo[3,4-b]quinoline, belonging to pyrazoloquinoline (PQ) family, likewise its regioisomeric products 10-R derivatives of 6-phenyl-6H-5,6,7-triazadibenzo[f,h]naphtho[3,2,1-cd]azulene representing cyclized seven-membered annulated azulene (AA) dyes. Cyclization of PQs into AAs is accompanied by a significant red shift of the first optical absorption band. This finding agrees with the results of quantum-chemical calculations performed by means of the semiempirical method PM3. As the solvent polarity rises all the dyes exhibit a blue shift of the first absorption band and a red shift of the fluorescence band. Such opposite trends in solvatochromic behavior have been reproduced within the semiempirical calculations in combination with the Lippert–Mataga dielectric polarization model. Depending on solvent polarity AA dyes emit light in the green, green–yellow or orange range of the visible spectrum what may be of interest for potential luminescent or electroluminescent applications.     

Phase transitions and temperature changes of the optical absorption edge in (NH2(C2H5)2)2CoCl4 layered crystal

This work was devoted to X-ray diffraction study and investigations of temperature changes of the optical absorption edge of (NH₂(C₂H₅)₂)₂CoCl₄ crystals in the region of possible phase transitions. The X-ray powder diffraction data revealed the monoclinic phase at room temperature – space group P2/n. The cobalt atom was found to be square-plane coordinated by four chlorine atoms resulting [CoCl₄]^2– anion, which is surrounded by two DEA⁺ cations. It was shown that the low-energy tail of the absorption edge in these materials possesses an exponential shape. In the temperature range above 255?K it follows the empirical Urbach’s rule. The obtained experimental data confirmed the existence of the ferroelastic phase in (NH₂(C₂H₅)₂)₂CoCl₄ in the temperature range between 255 and 326?K. The anomalous behaviour of the investigated parameters observed at the temperatures below 255?K would be related to earlier unknown phase transitions.     

Structural and magnetic phase transitions in (Chloroanilinium)2CuX4 (X = Cl, Br)

Successive structural phase transitions of (4-ClC₆H₄NH₃)₂CuCl₄, which occur in a very narrow temperature range were reinvestigated by Fourier transform nuclear quadrupole resonance (FT NQR) measurements. The phase transitions at 275.5 and 277.0 K were confirmed. The effect of the deuteration of the ammonium end on these transitions was studied. The³⁵Cl NQR frequencies of organic cation were observed to decrease by about 4 kHz and the phase transition temperatures to decrease by about 2 K by the deuteration, suggesting that the ?NH₃ ⁺ … Cl hydrogen bond is weakened by the deuteration. The magnetic phase transition temperature of 8.6 K showed no remarkable change within experimental error by the deuteration. It was found that the magnetically ordered state is broken by the radio-frequency magnetic field of about 15–35 Oe usually employed in pulsed NQR. However, in the deuterated compound (4-ClC₆H₄ND₃)₂CuCl₄, the ordered state was found to be stabler for the usual radiofrequency power. By combining with the NQR data of (4-ClC₆H₄NH₃)₂CuBr₄ and (3,5-Cl₂C₆H₃NH₃)₂CuCl₄, the possibility is discussed of tuning the interlayer interaction between the organic cation layer and the inorganic complex anion layer by the halogen substitution in the organic cation as well as by the halogen replacement in the inorganic complex anion.     

Dielectric permittivity and AC conductivity investigations of the structural phase transitions in (NH3)2(CH2)7CdCl2Br2

The AC dielectric permittivity as a function of temperature (100–400 K) at different frequencies (between 80 Hz and 20 kHz) for the layered alkylene diammonium insulator containing Cd, namely, [(NH₃)₂(CH2)₇CdCl₂Br₂] has been measured. The formation of the compound was confirmed by microchemical analysis and IR absorption spectrometry. X-ray powder diffraction indicates an orthorhombic unit cell of dimensions: a = 10.219(2) Å, b = 9.168(2) Å and c = 38.694(4) Å. The AC conductivity ([sgrave]) is presented as a function of temperature and frequency. The conductivity and permittivity results indicate the presence of first-order phase transitions at 317 and 345 K. This has been confirmed by thermal analysis techniques. The activation energies were of values ranging between 0.15 and 0.62 eV depending upon the temperature range and the applied frequencies.     

Measurement of wurtzite ZnO/rutile TiO2 heterojunction band offsets by x-ray photoelectron spectroscopy

Four novel dmit complexes: [(C₂H₅)₄N][Ni (dmit)₂], [(C₃H₇)₄N][Ni(dmit)₂], [(C₂H₅)₄N][Au(dmit)₂] and [(C₃H₇)₄N][Au(dmit)₂], abbreviated as EtNi, PrNi, EtAu, and PrAu, were synthesized. The third-order nonlinear optical properties of them in acetonitrile solutions were investigated by using the Z-scan technique with 20 ps pulses width at 1064 nm. When the on-axis irradiance at focus I ₀ was 5.025 GW/cm², the nonlinear refraction coefficient n ₂, the third-order nonlinear susceptibility χ ⁽³⁾, the molecular second-order hyperpolarizability γ of the four types of material were obtained with subject to Z-scan curves, and these indexes were with the magnitudes of 10⁻¹⁸ m²/W, 10⁻¹³ esu, and 10⁻³¹ esu, respectively. The nonlinear absorption coefficient β of Ni samples had the 10⁻¹² m/W scale. The impact of different metals and cations on the third-order nonlinear optical properties of materials was analyzed. Through the derivation, the result suggests that these dmit complexes are promising candidates for applications to nonlinear optical devices manufacture in the near-infrared waveband.     

Structural characterization,thermal, ac conductivity and dielectric properties of (C7H12N2)2[SnCl6]Cl2·1.5H2O

(C₇H₁₂N₂)₂[SnCl₆]Cl₂·1.5H₂O is crystallized at room temperature in the monoclinic system (space group P2₁/n). The isolated molecules form organic and inorganic layers parallel to the (a, b) plane and alternate along the c-axis. The inorganic layer is built up by isolated SnCl₆ octahedrons. Besides, the organic layer is formed by 2,4-diammonium toluene cations, between which the spaces are filled with free Cl^? ions and water molecules. The crystal packing is governed by means of the ionic N—H···Cl and Ow—H···Cl hydrogen bonds, forming a three-dimensional network. The thermal study of this compound is reported, revealing two phase transitions around 360(±3) and 412(±3) K. The electrical and dielectric measurements were reported, confirming the transition temperatures detected in the differential scanning calorimetry (DSC). The frequency dependence of ac conductivity at different temperatures indicates that the correlated barrier hopping (CBH) model is the probable mechanism for the ac conduction behavior.     

DFT(B3LYP/LanL2DZ), non-linear optical and electrical studies of a new hybrid compound: [C6H10(NH3)2]CoCl4·H2O

A new organic-inorganic material [C₆H₁₀(NH₃)₂]CoCl₄·H₂O was reported. The title compound was synthesized at room temperature by slow evaporation and then characterized by a single X-ray diffraction, spectroscopic measurements, thermal analysis and dielectric technique. It crystallizes in the non-centrosymmetric space group Pna2₁ with the following unit cell parameters: a=12.5328(1) Å, b=9.0908(1) Å, c=11.7440(1) and α=β=γ=90°. The structure can be described by the alternation of two different cationic-anionic layers. It consists of isolated H₂O, isolated [CoCl₄]²⁻ tetrahedral anions and diammoniumcyclohexane [C₆H₁₀(NH₃)₂]²⁺ cations, which are connected via N–H…Cl, N–H…O and O–H…N hydrogen bonds. The Hirshfeld surface analysis was conducted to investigate intermolecular interactions and associated 2D fingerprint plots, revealing the relative contribution of these interactions in the crystal structure quantitatively. Theoretical calculations were performed using DFT/B3LYP/LanL2DZ method for studying the molecular structure and vibrational spectra and especially to examine the non-linear optical behavior of the compound. Solid state ¹³C NMR spectrum shows three signals correspond to three different carbon environments. Thermal analysis discloses a phase transition at the temperature 315 K and the evaporation of water molecule at 327 K. A detailed dielectric study was reported and shows a good agreement with thermal measurements.     

Optical,structural characterization and dielectric relaxation of [C2H5NH3]2ZnCl4 compound

ABSTRACT

The new organic-inorganic compound [C₂H₅NH₃]₂ZnCl₄ has been grown by the slow evaporation at room temperature. The zero-dimensional (0-D) structure for this compound was determined by the single X-ray diffraction. It crystallizes at room temperature in the non-centrosymmetric space group Pna2₁ and consists of ethylammonium cations [C₂H₅NH₃]⁺ and [ZnCl₄]^2? tetrahedra anions. That is interconnected by means of hydrogen bonding contacts N-H···Cl. The molecular geometry and vibrational frequencies of [ZnCl₄]^2? and [C₂H₅NH₃]⁺ in the ground state was calculated using density functional method (B3LYP) with 6–31G(d) and 6–311G (d,p) basis set. The optimized geometric bond lengths and bond angles, obtained by using B3LYP/6–311G (d,p), show the best agreement with the experimental data. The optical absorbance was measured in order to deduce the absorption coefficient α, optical band gap E_g. The optical band gap is determined by extrapolating the plotted graph of (αhυ)^1/2 vs. (hυ). The large value of indirect optical band gap energy indicates the insulating nature of this material. Moreover, the extinction coefficient, refractive index and the dielectric permittivity of [C₂H₅NH₃]₂ZnCl₄ compound were calculated and the results are discussed. The evolution of the dielectric loss as a function of frequency revealed a distribution of relaxation times, probably ascribed to the reorientational dynamics of alkyl chains in this compound, and then analyzed with the Cole–Cole formalism.