1\text{}^{1}H NMR Study of Molecular Dynamics of 4-apyH Cation under High Hydrostatic Pressure

Polycrystalline [4-NH$\text{}_{2}$C$\text{}_{5}$H$\text{}_{4}$NH] SbCl$\text{}_{4}$ and [4-NH$\text{}_{2}$C$\text{}_{5}$H$\text{}_{4}$NH] SbCl$\text{}_{6}$ have been investigated by proton NMR methods between 120 K and 370 K under hydrostatic pressure of 0.1 and 520 MPa. Reduction in the dipolar second moment is interpreted in terms of cation reorientation. Activation energies characterizing the motion increase with increasing pressure

Reorientational dynamics of organic cations in perovskite-like coordination polymers

Here we report the dynamics of organic cations as guest molecules in a perovskite host-framework. The molecular motion of CH3NH3+ (MAFe), (CH3)2NH2+ (DMAFe) and (CH3)3NH+ (TrMAFe) in the cage formed by KFe(CN)63− units was studied using a combination of experimental methods: (i) thermal analysis, (ii) dielectric and electric studies, (iii) optical observations, (iv) EPR and 1H NMR spectroscopy and (v) quasielastic neutron scattering (QENS). In the case of MAFe and TrMAFe, the thermal analysis reveals one solid-to-solid phase transition (PT) and two PTs for the DMAFe crystal. A markedly temperature-dependent dielectric constant indicates the tunable and switchable properties of the complexes. Also, their semiconducting properties are confirmed by a dc conductivity measurement. The broadband dielectric relaxation is analyzed for the TrMAFe sample in the frequency range of 100 Hz–1 GHz. QENS shows that we deal rather with the localized motion of the cation than a diffusive one. Three models, which concern the simultaneous rotation of the CH3 and/or NH3 group, π-flips and free rotations of the organic cation, are used to fit the elastic incoherent structure factor. The 1H NMR spin–lattice relaxation time for all compounds under study, as well as the second moments, has been measured in a wide temperature range. In all studied samples, the temperature dependence of the second moment of the proton NMR line indicated the gradual evolution of the molecular movements from the rigid state up to a highly disordered on

Crystal structural analysis of methyl-substituted pyrazines with anilic acids: a combined diffraction, inelastic neutron scattering, 1 H-NMR study and theoretical approach

The crystal and molecular structures of (1) 2-methylpyrazine (2MP) with 2,5-dichloro-3,6-dihydroxy-p-quinone (chloranilic acid, CLA), (2) 2-methylpyrazine (2MP) with 2,5-dibromo-3,6-dihydroxy-p-quinone (bromanilic acid, BRA), (3) 2,3,5-trimethylpyrazine (TrMP) with 2,5-dichloro-3,6-dihydroxy-p-quinone (chloranilic acid, CLA), and (4) 2,3,5-trimethylpyrazine (TrMP) with 2,5-dibromo-3,6-dihydroxy-p-quinone (bromanilic acid, BRA) were analyzed in terms of the number of independent methyl groups in their crystal structure. The inelastic neutron back-scattering spectra at low temperature (4–40 K) were discussed in terms of methyl group tunnelling. The INS spectra were compared with the temperature dependence of the 1H-NMR spin–lattice relaxation time, particularly at low temperatures, where CH3 tunnelling is postulated. The infrared and Raman spectra at room temperature were recorded for all complexes under investigation. Furthermore, the vibrational spectra were discussed in terms of the structure of molecules and their interactions. The structural phase transition of the TrMP·CLA complex at 171/175 K (cooling/heating) was characterized by DSC and single-crystal X-ray diffraction. Full-geometry optimization was carried out in the solid state in order to obtain the minimum structures and bonding properties. The results are in very good agreement with the experimental data. The infrared spectrum in the harmonic approximation was calculated and a comparative vibrational analysis was performed. CRYSTAL09 vibrational results appear to be in good agreement with the experimental result

Organic-inorganic hybrid crystals, (2,4,6-CH 3 PyH) 3 Sb 2 Cl 9 and (2,4,6-CH 3 PyH) 3 Bi 2 Cl 9 . Crystal structure characterization and tunneling of CH 3 groups studied by 1 H NMR and neutron spectroscopy

The crystal structures of (2,4,6-CH3PyH)3Sb2Cl9 (TMPCA) and (2,4,6-CH3PyH)3Bi2Cl9 (TMPCB) (Py – pyridine) have been determined at 100 K by the single crystal X-ray diffraction method. TMPCA and TMPCB crystallize in the monoclinic C2/c and triclinic P1 polar space group, respectively. In both cases the asymmetric part is comprised of three nonequivalent 2,4,6-trimethylpyridinium cations and a discrete M2Cl93− anion. The Bi2Cl93− moiety forms a face-sharing bi-octahedron, whereas in a case of Sb2Cl93− we deal with two pyramids connected by a corner. The inelastic neutron scattering spectra (INS) were recorded for TMPCA at low temperatures (4–50 K). Two peaks on each side of the central elastic line have been observed at ca. 4.8 and 2.9 μeV, the high energy peak exhibits an excitation energy value equal to ca. 6 meV. For TMPCA and TMPCB the 1H NMR spin–lattice relaxation times, T1, have been measured in the temperature region 15–410 K. The flattening of the T1 (spin–lattice) vs. reciprocal temperature, 1/T, dependence between 30 K and 15 K indicates the incoherent tunneling effect of the methyl group being treated as the quantum rotor. The conclusions drawn from the 1H NMR results as regards to the tunneling of the CH3 groups in the pyridinium cations are consistent with the tunneling peaks observed in the INS spectra

Structure and tunneling splitting spectra of methyl groups of tetramethylpyrazine in complexes with chloranilic and bromanilic acids

The crystal and molecular structure of the 2,3,5,6-tetramethylpyrazine (TMP) complex with 2,5-dibromo-3,6-dihydroxy-p-quinone (bromanilic acid, BRA) has been studied and the results are compared with TMP CLA (2,5-dichloro-3,6- dihydroxy-p-quinone (chloranilic acid, CLA) complex. The X-ray structure of TMP BRA complex indicates the formation of dimeric units, in which two BRA - anions are connected by two O-H···O (2.646(2) Å) hydrogen bonds, whereas the cations and anions are joined together by strong N+-H···O- (2.657(2) Å) hydrogen bonds. The results are analyzed in terms of both the methyl group surroundings and the C-H···O and N+- H···O- (or N···H-O) bridge formations. Both effects, the strength of the N+- H···O- hydrogen bonds and steric hindrance for the rotations, are responsible for the CH3 group dynamics. For the TMP CLA and TMP BRA complexes, the inelastic neutron backscattering spectra were also investigated. In the case of TMP CLA, four tunneling signals have been observed in the energy range ±30 ÎeV, which indicates four inequivalent methyl groups in the crystal structure at the lowest temperature. No tunneling splitting is observed in the case of the TMP BRA complex, most probably due to the overlapping with the elastic peak. The tunneling results are consistent with the 1H NMR spin-lattice relaxation time investigations in a wide temperature range, which also point to the CH 3 group tunneling effect in the case of TMP CLA. © 2014 American Chemical Society

Structures and phase transitions in neat 4,4′-di- tert -butyl-2,2′-bipyridyl and in its molecular complexes with either bromanilic or iodanilic acid

Using the DSC method, structural phase transitions have been found at 165 and 219 K for 4,4′-di-tert-butyl-2,2′-bipyridyl (dtBBP), whereas for its complex with iodanilic acid (dtBBP·IA), its phase transition is at 331 K. For the other molecular complex described (with bromanilic acid, dtBBP·BRA), no phase transitions have been observed between the liquid nitrogen temperature and the temperature of crystal decomposition. The crystal structures of the neat dtBBP have been determined at 130, 190 and 250 K, whereas for its molecular complex with bromanilic acid (BRA) is determined at 150 K and for its complex with iodanilic acid (IA) determined at 293 and 345 K. The crystal structure of neat dtBBP is characterized by layers of molecules, which are grouped by their t-butyls. The structures of dtBBP·BRA and dtBBP·IA are analogous to one another and consist of infinite chains of alternating acid and base molecules linked by hydrogen bonds. On the basis of the structural, dielectric and spectroscopic results (infrared and Raman), the mechanisms of the phase transitions have been proposed for dtBBP and dtBBP·IA. The 1H NMR spin–lattice relaxation times for all compounds under study, as well as the second moment for the neat dtBBP in a wide temperature, have been measured. The anomalies in the temperature dependent infrared spectra together with the NMR results support the supposition that for dtBBP the dynamics of tert-butyl groups is responsible for the mechanism of the phase transitions found. The dynamics of the molecules in the crystals presented is related to the rotation both of the methyl and tert-butyl groups

The relationship between reorientational molecular motions and phase transitions in [Mg(H2O)6](BF4)2[Mg(H_2O)_6](BF_4)_2, studied with the use of 1H^{1}H and 19F^{19}F NMR and FT-MIR

A 1H and 19F nuclear magnetic resonance study of [Mg(H2O)6](BF4)2 has confirmed the existence of two phase transitions at T c1 ≈ 257 K and T c2 ≈ 142 K, detected earlier by the DSC method. These transitions were reflected by changes in the temperature dependences of both proton and fluorine of second moments M2 H and M2 F and of spin-lattice relaxation times T1 H and T1 F. The study revealed anisotropic reorientations of whole [Mg(H2O)6]2+ cations, reorientations by 180° jumps of H2O ligands, and aniso- and isotropic reorientations of BF4 − anions. The activation parameters for these motions were obtained. It was found that the phase transition at T c1 is associated with the reorientation of the cation as a whole unit around the C3 axis and that at T c2 with isotropic reorientation of the BF4 − anions. The temperature dependence of the full width at half maximum value of the infrared band of ρt (H2O) mode (at ∼596 cm−1) indicated that in phases I and II, all H2O ligands in [Mg(H2O)6]2+ perform fast reorientational motions (180° jumps) with a mean value of activation energy equal to ca 10 kJ mole−1, what is fully consistent with NMR results. The phase transition at T c1 is associated with a sudden change of speed of fast (τR ≈ 10−12 s) reorientational motions of H2O ligands. Below T c2 (in phase III), the reorientations of certain part of the H2O ligands significantly slow down, while others continue their fast reorientation with an activation energy of ca 2 kJ mole−1. This fast reorientation cannot be evidenced in NMR relaxation experiments. Splitting of certain IR bands connected with H2O ligands at the observed phase transitions suggests a reduction of the symmetry of the octahedral [Mg(H2O)6]2+ complex cation

Isostructural phase transition, quasielastic neutron scattering and magnetic resonance studies of a bistable dielectric ion-pair crystal [(CH3)2 NH2]2 KCr(CN)6

We have synthesised and characterised a novel organic–inorganic hybrid crystal, [(CH3)2NH2]2KCr(CN)6. The thermal DSC, TMA, DTG and DTA analyses indicate two solid-to-solid structural phase transitions (PTs). According to the X-ray diffraction experiments, the first PT at 220 K is isostructural, since it does not involve a change of the space group. This transition occurs between the states, where the (CH3)2NH2+ cations are orientationally disordered and ordered (frozen). The other reversible PT at 481 K leads to a melt-like phase similar to the one observed in plastic crystals or polar liquids. Dielectric spectroscopy has been used to characterise the switching properties of the dipole moments in the vicinity of the PTs. Continuous-wave electron paramagnetic resonance spectroscopy was employed to investigate the effect of ordering on the local environment of the Cr3+ ions. We have also applied the quasielastic neutron scattering (QENS) technique as well as 1H NMR spectroscopy to measure the dynamics of the (CH3)2NH2+ cations residing in the inorganic framework