A. Piecha-Bisiorek

Structure–property relationships in hybrid (C3H5N2)3[Sb2I9] and (C3H5N2)3[Bi2I9] isomorphs

Two hybrid crystals imidazolium iodoantimonate(III) and iodobismuthate(III), (C3H5N2)3[Sb2I9] (ImIA) and (C3H5N2)3[Bi2I9] (ImIB), have been synthesized and characterized in a wide temperature range (100–350 K) by means of X-ray diffraction, dielectric spectroscopy, proton magnetic resonance (1H NMR), FT-IR spectroscopy and optical observations. They undergo two temperature induced solid–solid structural phase transitions. The first one, quasi-continuous (with temperature hysteresis below 1 K), occurs at 324 K in ImIA and 327 K in ImIB, and the second one, clearly of the first order, at 273/278 (cooling/heating) and 291/295 K, in ImIA and ImIB, respectively. Ferroelastic properties are maintained in low-temperature phases. Both materials are isomorphic in the corresponding phases. High temperature phase I has a hexagonal P63/mmc symmetry, and phase II has orthorhombic Cmcm. The crystal architecture is composed of discrete, face-sharing bioctahedra [M2I9]3− (M: Sb, Bi) and imidazolium cations which are highly disordered over phases I and II. The dynamics of the imidazolium cations has a prominent impact on the stability of the particular phases.

Strong Improper Ferroelasticity and Weak Canted Ferroelectricity in a Martensitic-Like Phase Transition of Diisobutylammonium Bromide

Diisobutylammonium bromide is found to be a unique improper ferroelastic in which the elastic degrees of freedom seem to play the essential role, giving rise to a domain pattern resembling that of martensitic phase transitions. A weak canted ferroelectricity turns out switchable by an electric field.

Polar and antiferroelectric behaviour of a hybrid crystal – piperazinium perchlorate

Monoprotonated piperazinium perchlorate, [NH2(CH2)4NH][ClO4], appeared to be a novel room temperature polar material (P1). Its acentric symmetry was confirmed by single-crystal X-ray diffraction, second harmonic generation (SHG) and pyroelectric measurements. Differential scanning calorimetry (DSC) measurements revealed a complex sequence of phase transitions above room temperature: I ↔ II at 433/422 K (heating–cooling), II ↔ III at 417/411 K, III ↔ IV at 403/395 K and IV ↔ V at 397 K (the lowest temperature phase transition recorded only upon heating). The characteristic feature of the structure of [NH2(CH2)4NH][ClO4] is the presence of two parallel cationic chains which are connected with each other by strong N–H⋯N hydrogen bonds. In phase V, these strongly polar non-equivalent chains contribute to spontaneous polarization. 1H NMR measurements disclosed the reorientational motions of the piperazinium ([NH2(CH2)NH]+) cations as well as the proton motion in the N–H⋯N hydrogen bonds along the piperazine chain. Over phase I, the overall motions of the ClO4− anions and reorientational motion of cations are postulated. The dielectric response, e′(T), accompanying the PT I ↔ II indicates possible antiferroelectricity in phase II.

Enormous lattice distortion through an isomorphous phase transition in an organic–inorganic hybrid based on haloantimonate(III)

Bis(diisobutylammonium) octabromodiantimonate(III), [(i-C4H9)2NH2]2Sb2Br8, has been synthesized. The differential scanning calorimetric measurements indicate a reversible, first-order phase transition at 222/229 K (cooling/heating). The single crystal X-ray diffraction studies reveal that the phase transition is isomorphous and is accompanied by a huge distortion of the crystal lattice. By comparison of the crystal structures of [(i-C4H9)2NH2]2Sb2Br8 and [(i-C4H9)2NH2]2Sb2Cl8, an analogous mechanism of the phase transition of the former is proposed. The change of the electronic structure of the complex during the phase transition was analyzed by UV-vis spectroscopy. A low-frequency dielectric relaxation process appears over phase I (below the room temperature) and corresponds to the dynamics of dipolar diisobutylammonium cations. The detailed analysis of the molecular motions of the organic cations studied by means of proton magnetic resonance (1H NMR) in a wide temperature range indicates a leading role of the methyl groups in the relaxation mechanism. A variable-temperature investigation of the infrared spectra of [(i-C4H9)2NH2]2Sb2Br8 confirms, in turn, the influence of the diisobutylammonium cation dynamics on the molecular mechanism of the structural transformation at 229 K.

Dynamics of Ferroelectric Bis(imidazolium) Pentachloroantimonate(III) by Means of Nuclear Magnetic Resonance 1H Relaxometry and Dielectric Spectroscopy

Some of haloantimonates(III) and halobismuthates(III) are ferroelectric. Bis(imidazolium) pentachloroantimonate(III), (C3N2H5)2SbCl5 (abbreviation: ICA) is the first example of such compounds with a one-dimensional anionic chain which exhibits ferroelectric properties. The relation between the ionic dynamics and network structure and the ferroelectric features is not clear. Here Nuclear Magnetic Resonance (NMR) (1)H spin-lattice relaxation experiments at 25 MHz are reported for ICA in the temperature range of 80 K-360 K, covering ferroelectric-paraelectric and structural phase transitions of the compound occurring at 180 and 342 K, respectively. The relaxation process is biexponential in the whole temperature range indicating two dynamically nonequivalent types of imidazolium cations. Temperature dependences of both relaxation contributions allow for identifying three motional processes. Two of them are cation-specific - i.e. they are attributed to the two types of imidazolium cations, respectively. The third process involves both types of cations, and it is characterized by much lower activation energy. Moreover, the relaxation data (combined with (1)H second moment measurements) show that the ferroelectric-paraelectric phase transition mechanism is governed, to a large extent, by the anionic network arrangement. The NMR studies are complemented by dielectric spectroscopy experiments performed in the vicinity of the Curie temperature, TC = 180 K, to get insight into the mechanism of the ferroelectric-paraelectric phase transition. The dielectric dispersion data show critical slowing down of the macroscopic relaxation time, τ, in ICA when approaching TC from the paraelectric side, indicating an order-disorder type of ferroelectrics.

Phase sequence in diisopropylammonium iodide: avoided ferroelectricity by the appearance of a reconstructed phase

Crystals of diisopropylammonium iodide are synthesized, grown and characterized. Two phases: P21/m (Z = 1) and P212121 (Z = 2) are observed. In contrast with analogous compounds no polar phase occurs, despite a critical-like electric behaviour. A phenomenological theory is proposed to describe the thermodynamics of the whole family of diisopropylammonium halides.

Ferroelectricity in bis(ethylammonium) pentachlorobismuthate(III): synthesis, structure, polar and spectroscopic properties

A brief description of the thermal, structural and dielectric properties of bis(ethylammonium) pentachlorobismuthate(III) ferroelectric with Ps that equals to 1.4 μC cm−2 at 180 K is presented. This paper focuses in particular on the molecular mechanism of a phase transition that is related mainly to the deformation of the anionic sublattice confirmed by temperature-variable powdered UV-Vis spectroscopy.

Physical and Structural Characterization of Imidazolium-Based Organic–Inorganic Hybrid: (C3N2H5)2[CoCl4]

(C3N2H5)2[CoCl4] (ICC) was characterized in a wide temperature range by the single-crystal X-ray diffraction method. Differential scanning calorimetry revealed two structural phase transitions: continuous at 245.5 K (from phase I to II) and a discontinuous one at 234/237 K (cooling/heating) (II → III). ICC adopts monoclinic space groups C2/c and P21/c in phase (I) and (III), respectively. The intermediate phase (II) appears to be incommensurately modulated. Dynamic properties of polycrystalline ICC were studied by means of dielectric spectroscopy and proton magnetic resonance ((1)H NMR). The presence of a low frequency dielectric relaxation process in phase III reflects libration motion of the imidazolium cations. The temperature dependence of the (1)H spin-lattice relaxation time indicated two motional processes with similar activation energies that are by about an order of magnitude smaller than the activation energy obtained from dielectric studies. There are no abrupt changes in the (1)H relaxation time at the phase transitions indicating that the dynamics of the imidazolium rings gradually varies with temperature; that is, it does not change suddenly at the phase transition. Negative values of the Weiss constant and the intermolecular exchange parameter were obtained, confirming the presence of a weak antiferromagnetic interaction between the nearest cobalt centers. Moreover, the magnitude of zero field splitting was determined. The AC susceptibility measurements show that a slow magnetic relaxation is induced by small external magnetic field.

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 μeV, 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 (1)H NMR spin-lattice relaxation time investigations in a wide temperature range, which also point to the CH3 group tunneling effect in the case of TMP CLA.

Ferroelasticity and piezoelectricity of organic–inorganic hybrid materials with a one-dimensional anionic structure: so similar, yet so different

The synthesis, structural aspects, thermal and dielectric analysis for new members of the ferroic family, polynuclear Bi(III) and Sb(III) halide complexes based on a pyrazolium cation with the formulas (C3N2H5)[BiCl4]·H2O and (C3N2H5)[SbCl4]·H2O, are presented. The former compound was found to undergo a ferroic phase transition of the ferroelastic type at 213/219 K (cooling/heating scans), whereas, the latter one exhibited a piezoelectric feature in the dielectric response function. The molecular motions of pyrazolium cations were analyzed based on the spin–lattice relaxation time of 1H NMR measurements.