1H NMR studies on molecular motions of 4-aminopyridinium and pyrrolidinium cations in new ferroics

The aim of the study was to check the effect of the cation on the molecular dynamics of the anion, which is not directly observed, in different phases of the following compounds: (C4H8NH2)SbCl6(C4H8NH2)Cl, (C4H8NH2)SbCl6 and (4-apyH)ClO4, (4-apyH)SbCl4.     

1H NMR study of molecular dynamics and phase transition in (NH4)2ZnBr4

The proton second moment (M ₂) and spin-lattice relaxation time (T ₁) have been measured in (NH₄)₂ZnBr₄ in the range 77–300 K. The room-temperature spectrum shows a structure which disappears around 243 K. The signal is strong and narrow even at 77 K. Proton T ₁ shows a maximum at 263 K, caused by spin rotation interaction and decreases with decreasing temperature till 235 K, where it shows a sudden increase. Below 235 K, again it decreases and shows a slope change around 216.5 K (reported T_c ). From 216.5 K, T ₁ decreases continuously without exhibiting any minimum down to 77 K. The narrow line at 77 K, and absence of a T ₁ minimum down to 77 K indicate the possibility of quantum mechanical tunnelling in this system. Motional parameters such as activation energy and pre-exponential factor have been evaluated for the reorientational motion of the NH⁺ ₄ ion.     

Heteronuclear and quadrupolar second moment determination of the NQR line of 127I in NaIO4

This work reports on a theoretical expression of the heteronuclear dipolar second moment (M2IS) of a NQR line of spin 5/2 nuclei. The result is applied to obtain M2IS for the resonance line of 127I in NaIO4, and in addition, an indirect determination of the quadrupolar second moment is given.     

Molecular dynamics in ferroelectric 4-aminopyridinium tetrachloroantimonate(III), [4-NH2C5H4NH][SbCl4

Proton spin-lattice relaxation time and second moment of polycrystalline [4-NH2C5H4NH][SbCl4] have been determined at 160-400 K, at 90 and 25 MHz. The temperature dependence of the second moment indicates that the cation is in the "frozen" state over that temperature range, while at higher temperatures it oscillates at an angle of 135 degrees to the pseudo-six-fold axis of the aromatic ring. Weak influence of different phase transitions on the temperature dependences of relaxation times T1 and T1D can be explained in terms of molecular dynamics.     

35Cl NQR and2H NMR analysis of the critical dynamics close to the displacive normal-incommensurate phase transition in an organic crystal

Nuclear magnetic resonance (NMR) experiments,³⁵C1 nuclear quadrupole resonance (NQR) and²H NMR, have been performed close to the displacive normal-incommensurate phase transition in the organic crystal of bis-(4-chlorophenyl)-sulfone. Calculations using coherent neutron scattering results show that the soft-mode contribution cannot explain the rapid increase of the spin-lattice relaxation rates close to the transition temperature. Calculations of the spectral densities taking into account the existence of a central-peak phenomenon describe both³⁵C1 NQR and²H NMR spin-lattice relaxation rates on approaching the phase transition. In this way, the width of the central peak can be estimated to be in the range of several gigahertz.     

NMR and NQR studies on superconducting Sr2RuO4

We review our nuclear-magnetic resonance (NMR) and nuclear-quadrupole-resonance (NQR) studies in superconducting Sr₂RuO₄, which have been performed in order to investigate the gap structure and the pairing symmetry in the superconducting state and magnetic fluctuations in the normal state. The spin-lattice relaxation rate (1/T₁) of a high-quality sample with shows a sharp decrease without a coherence peak just below T_c, followed by a T³ behavior down to 0.15 K. This result indicates that the superconducting gap in pure Sr₂RuO₄ is a highly anisotropic character with a line-node gap. The Knight shift, which is related to the spin susceptibility, is unchanged in the superconducting state irrespective of the direction of the applied fields and various magnitude of the field. This result strongly suggests that the superconducting pairs are in the spin-triplet state, and the spin direction of the triplet pairs is considered to be changed by small fields of several hundred Oe.     

含羟基的3-苯基-4(1H)-喹啉酮衍生物的1H NMR

在抗骨质疏松药物的设计中,根据电子等排原理和药物的构效关系理论,设计并同时合成了7-羟基-3-苯基-4(1H)-喹啉酮新衍生物以及其同分异构体5-羟基-3-苯基-4(1H)-喹啉酮新衍生物.本文报道上述新化合物的¹H NMR数据.     

Crystal structure and electrical properties study of 4-aminopyridinium chloridobismuthate (III) (C5N2H7)4.HBi2Cl11

The crystal structure of (C₅N₂H₇)₄.HBi₂Cl₁₁ has been determined at room temperature by single crystal X-ray diffraction. The compound crystallizes in the triclinic system with Pī space group. The crystal structure consists of two asymmetric inequivalent molecules of 4-aminopyridinium and anionic HBi₂Cl₁₁ chains. The HBi₂Cl₁₁ anionic chains stacked along the a-axis are formed with Bi₂Cl₁₁ dimers connected to each other via hydrogen atoms. The crystal packing is stabilized with N–H...Cl hydrogen bonds connecting aminopyridinium units to the HBi₂Cl₁₁ anionic chains. The title compound exhibits an order–disorder phase transition at 338 K. The AC electrical conductivity properties of (C₅N₂H₇)₄.HBi₂Cl₁₁ compound have been investigated by means of impedance spectroscopy measurements over wide ranges of frequencies and temperatures, 200 Hz to 5 MHz and 303 to 418 K, respectively. Detailed analysis of the impedance spectrum suggests that the electrical properties of the material are strongly temperature dependent. The frequency-dependent conductivity data were fitted in the Jonscher's law: $ \sigma \left( \omega \right) = \sigma (0) + A{\omega^n} $ . The nature of variation of DC conductivity suggests Arrhenius type of electrical conductivity.     

1H and 13C NMR studies of molecular dynamics in the biocopolymer of glycolide and epsilon-caprolactone

Copolymers of glycolide and epsilon-caprolactone were studied using differential scanning calorimetry and solid-state NMR. The variation of the T1 relaxation time with temperature reflects local disorder and can be quantified in terms of the distribution of correlation times predicted by the Davidson-Cole model. T, relaxation is dominated by trans-gauche isomerisation, with an activation energy of 34-35 kJ mol(-1).     

NMR and NQR studies of spin dynamics and superconductivity in High-T c oxides

The magnetic and superconducting properties in the high-T _c cuprates have been investigated over a wide hole doping range by⁶³Cu,¹⁷O and²⁰⁵Tl NMR and NQR in the lightly-doped La_2?xSr_xCuO₄ (LSCO), the heavily-doped Tl₂Ba₂CuO_6+y (TBCO) and the Zn-doped YBa₂Cu₃O₇ (YBCO₇). In low doping region, the large antiferromagnetic (AF) spin correlation around the zone boundary (q=Q) causes the Curie-Weiss behavior of⁶³(1/T ₁ T) associated with that of the staggered susceptibility χ_O(T) in LSCO. In the vicinity of the hole content whereT _c has a peak, the AF spin correlation still survives, although the magnetic coherence length ξ_M is considerably short being presumably (ξ_M/a) ～ 1. The further doping destroys progressively the AF spin correlation, which is no longer present is non-superconducting TBCO compounds. These NMR evidences signify that there is an intimate relation between the presence of the AF spin correlation and the onset of the superconductivity. The local collapse of AF spin correlation is a primary cause for the unexpected strong reduction ofT _c in case of the substitution of Zn impurities into the CuO₂ plane. The superconducting properties clarified by NMR experiments cannot be accounted for by the conventional BCS model or other isotropic s-wave models. A d-wave model is applicable in interpreting consistently most of the NMR results, if the finite density of states at the Fermi level is taken into consideration and is associated with the pair breaking effect. There are increasing evidences that the magnetic mechanism for the superconductivity is promising in high-T _c cuprates.     

Influence of moisture on molecular motion in nylon 4 studied by NMR

A proton nuclear magnetic resonance (NMR) in solid poly-2-pyrrolidone (Nylon 4) was studied at temperatures between –165 C and 185 C. Wideline NMR spectra were measured on powdered samples of dry Nylon 4 and of moist Nylon 4. The second momentsM ₂ were calculated and likewise an analysis of the spectra according to K. Bergmann and K. Nawotki was performed for the purpose of the study of molecular motion in these samples. The second moment and the linewidth decrease with an increasing temperature. This fact testifies to an increasing intensity of molecular motion. It was found out that molecular motion is influenced by the presence of water and of low molecular fractions of the polymer. The presence of both factors is manifested by the decrease of theM ₂ values at temperatures higher than –60 C. It was found out from the analysis of the NMR spectra that processes in noncrystalline ( _a) and crystalline ( _c) regions of the dry sample start at 110 C. Crystallinity calculated by means of analysis of the spectra is 0·29. This value is in good agreement with the result obtained from the X-ray measurements.     

35Cl NQR and XRD Studies on Cs2[Ag(I) x Au(I)1 − x Cl2][Au(III)Cl4]

³⁵Cl NQR and XRD have been investigated on the solid solution Cs₂[Ag(I) _x Au(I)_1???x Cl₂][Au(III)Cl₄] which yielded NQR lines by annealing. The crystal forms a tetragonal cell in the whole range of x. However, a change of the modification occurs at x?≈?0.85. The increase of c and decrease of a were observed in the range of 0.0?≤?x?≤?0.7.     

A 2H and 14N NMR study of molecular motion in polycrystalline choline salts

²H and ¹⁴N solid-state NMR spectra of polycrystalline choline chloride, bromide, and iodide indicate that 180° cation flipping motion occurs in all three salts. From the temperature dependence of these spectra, the activation energy for this motion is determined to be 5.8 ± I kcal/mol in the iodide salt and 11 ± 1.5 kcal/mol in the chloride salt. In the bromide salt the reorientation rate is too rapid to be determined from the NMR lineshape, but the temperature dependence of the ²H quadrupole coupling parameters is indicative of a second-order phase transition at approximately 273 K. The spectral distortions in the ¹⁴N NMR spectra of the chloride and iodide salts are adequately explained using the motional model derived from the ²H NMR results, while the ¹⁴N spectra of the bromide salt show no motional effects. The axis of reorientation which is inferred from these data appears to be consistent with that indicated in a previous X-ray crystallographic study.     

Polymorphic phase transition and thermal stability in squaric acid (H2C4O4)

Phase transformations in squaric acid (H₂C₄O₄) have been investigated by thermogravimetry and differential scanning calorimetry with different heating rates β. The mass loss in TG apparently begins at onset temperatures T_di=245±5 °C (β=5 °C min^?1), 262±5 °C (β=10 °C min^?1), and 275±5 °C (β=20 °C min^?1). A polymorphic phase transition was recognized as a weak endothermic peak in DSC around 101 °C (T_c⁺). Further heating with β=10 °C min^?1 in DSC revealed deviation of the baseline around 310 °C (T_i), and a large unusual exothermic peak around 355 °C (T_p), which are interpreted as an onset and a peak temperature of thermal decomposition, respectively. The activation energy of the thermal decomposition was obtained by employing relevant models. Thermal decomposition was recognized as a carbonization process, resulting in amorphous carbon.     

1H NMR study of proton dynamics in (NH4)3H(SO4)2

Proton dynamics in (NH₄)₃H(SO₄)₂ has been studied by means of ¹H solid-state NMR. The ¹H magic-angle-spinning (MAS) NMR spectra were traced at room temperature (RT) and at Larmor frequency of 400.13 MHz. ¹H static NMR spectra were measured at 200.13 MHz in the range of 135–490 K. ¹H spin-lattice relaxation times, T₁, were measured at 200.13 and 19.65 MHz in the ranges of 135–490 and 153–456 K, respectively. The ¹H chemical shift for the acidic proton (14.7 ppm) indicates strong hydrogen bonds. In phase III, NH₄⁺ reorientation takes place; one type of NH₄⁺ ions reorients with an activation energy (E_a) of 14 kJ mol^− 1 and the inverse of a frequency factor (τ₀) of 0.85 × 10^− 14 s. In phase II, a very fast local and anisotropic motion of the acidic protons takes place. NH₄⁺ ions start to diffuse translationally, and no proton exchange is observed between NH₄⁺ ions and the acidic protons. In phase I, both NH₄⁺ ions and the acidic protons diffuse translationally. The acidic protons diffuse with parameters of E_a = 27 kJ mol^− 1 and τ₀ = 4.2 × 10^− 13 s. The translational diffusion of the acidic protons is responsible for the macroscopic proton conductivity, as the NH₄⁺ translational diffusion is slow and proton exchange between NH₄⁺ ions and the acidic protons is negligible.     

H/D isotope effect of 1H MAS NMR spectra and 79Br NQR frequencies of piperidinium p-bromobenzoate and pyrrolidinium p-bromobenzoate

H/D isotope effects onto ⁷⁹Br NQR frequencies of piperidinium p-bromobenzoate were studied by deuterium substitution of hydrogen atoms which form two kinds of N–H?O type hydrogen bonds, and the isotope shift of ca. 100 kHz were detected for a whole observed temperature range. In addition, ¹H MAS NMR spectra measurements of piperidinium and pyrrolidinium p-bromobenzoate were carried out and little isotope changes of NMR line shape were detected. In order to reveal effects of molecular arrangements into the obtained isotope shift of NQR frequencies, single-crystal X-ray measurement of piperidinium p-bromobenzoate-d2 and density-functional-theory calculation were carried out. Our estimation showed the dihedral-angle change between piperidine and benzene ring contributes to isotope shift rather than those of N–H lengths by deuterium substitution.     

17O NQR study of the ferroelectric phase transition in PbHPO4

The temperature dependence of the ¹⁷O NQR spectra of the O-H---O bonded oxygens in PbHPO₄ have been studied using a proton-¹⁷O double resonance technique. The results show that the protons move between two off-centre sites above T_c and freeze into one of the possible equilibrium sites below T_c.