On polarization in ionic crystals

Permittivities (ɛ) of LiF, NaCl, and KBr ionic crystals of various dispersities were measured. A progressive increase of ɛ up to ∼10⁵ with the dispersity of crystals was detected. A conclusion was drawn that this effect needs to be considered when determining effective charges on atoms by Szigeti’s method in the case of measuring ɛ of the powders.     

Covalent bonds in ionic crystals

An ion at a tetrahedral site will develop an induced octupole moment, which is equivalent to a covalent bond. The magnitude of this bond is calculated For AgI and the copper halides, and removes a discrepancy between theory and experiment which has stood for 47 years.     

1,10-Phenanthrolinium ionic liquid crystals

The 1,10-phenanthrolinium cation is introduced as a new building block for the design of ionic liquid crystals. 1,10-Phenanthroline, 5-methyl-1,10-phenanthroline, 5-chloro-1,10-phenanthroline, and 4,7-diphenyl-1,10-phenanthroline were quaternized by reaction with 1,3-dibromopropane or 1,2-dibromoethane. The resulting cations were combined with dodecyl sulfate or dioctyl sulfosuccinate anions. The influence of both the cation and anion type on the thermal behavior was investigated. Several of the complexes exhibit mesomorphic behavior, with smectic E phases for the dodecyl sulfate salts and smectic A phases for the dioctyl sulfosuccinate salts. Structural models for the packing of the 1,10-phenanthrolinium and anionic moieties in the liquid-crystalline phases are presented. The ionic compounds show fluorescence in the solid state and in solution.     

Metal-containing ionic liquids and ionic liquid crystals based on imidazolium moiety

Ionic liquids and ionic liquid crystals of imidazolium salts composed of various transition and main group metals have been reviewed. Ionic metal complexes of imidazoles and N-heterocyclic carbenes possess the similar properties were also included. These types of ILs and ILCs have been realized as potential solvents, catalysts, catalyst precursors and reagents for many organic transformations and provide ecofriendly protocols. They have also been found to play key roles in material science. Many of these IL systems are air- and moisture stable and are considered as alternatives for air- and moisture sensitive chloroaluminate-based ILs.     

Interfacial free energies of ionic crystals

Minimum values of the liquid-crystal interfacial free energy have been obtained from data on the maximum supercooling of small droplets of solutions of ionic crystals.     

Lorentz factors and surface permittivity of ionic crystals

The explicit analytical expressions and the corresponding numerical scheme are proposed for the calculation of Lorentz factors (LF) in ideal ionic crystals. Formulae for the permittivity tensors and local fields based on the calculated LF are given for a number of crystal types, including such as CsCl, NaCl, CaF₂ and ZnS, where Clausius–Mossotti and the addition rules are valid, and others, like Cu₂O, TiO₂, perovskite, wurtzite where the violation of both rules is common. The equations for the wave-vector-dependent permittivity in infinite crystals and for surface and lone layer permittivity are derived, and sample numerical calculations of the bulk, surface, and single layer permittivity are in a reasonable agreement with the data of measurements if the crystal structure parameters and ions' polarizabilities are used as the input data.     

Binding in purely ionic univalent crystals

A simple expression for the crystal lattice energy of A(I)B(VII) crystals is proposed using an indeterminacy principle. The suggested approach gives acceptable results.     

Preliminary communication Hydrogen-bonded ionic liquid crystals

Ionic and non-ionic building units were connected via hydrogen bonds. Stable liquid crystalline phases were obtained by a suitable choice of the units. The ionic associates are not miscible with the respective non-ionic associates.     

X-Ray scattering study of ionic colloidal crystals

The scattering study of ionic colloidal crystals by using one- and two-dimensional ultra-small-angle scattering techniques is reviewed with a special reference to dilute dispersions. Because of large lattice constants of colloidal crystals, ultra-small angle regions need to be covered either by long distance optical systems combined with a synchrotron X-ray source or by adopting the Bonse–Hart optics. The crystal structure, lattice constant, and crystal orientation can be precisely determined.     

Surface-functionalized ionic liquid crystal-supported ionic liquid phase materials: ionic liquid crystals in mesopores

The influence of confinement on the ionic liquid crystal (ILC) [C(18)C(1)Im][OTf] is studied using differential scanning calorimetry (DSC), polarized optical microscopy (POM), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The ILC studied is supported on Si-based powders and glasses with pore sizes ranging from 11 to 50 nm. The temperature of the solid-to-liquid-crystalline phase transition seems mostly unaffected by the confinement, whereas the temperature of the liquid-crystalline-to-liquid phase transition is depressed for smaller pore sizes. A contact layer with a thickness in the order of 2 nm is identified. The contact layer exhibits a phase transition at a temperature 30 K lower than the solid-to-liquid-crystalline phase transition observed for the neat ILC. For applications within the "supported ionic liquid phase (SILP)" concept, the experiments show that in pores of diameter 50 nm a pore filling of α>0.4 is sufficient to reproduce the phase transitions of the neat ILC.     

Synthesis and mesomorphic properties of rigid-core ionic liquid crystals

Ionic liquid crystals combine the unique solvent properties of ionic liquids with self-organization found for liquid crystals. We report a detailed analysis of the structure-property relationship of a series of new imidazolium-based liquid crystals with an extended aromatic core. Investigated parameters include length and nature of the tails, the length of the rigid core, the lateral substitution pattern, and the nature of the counterion. Depending on the molecular structure, two mesophases were observed: a bilayered SmA2 phase and the more common monolayered SmA phase, both strongly interdigitated. Most materials show mesophases stable to high temperatures. For some cases, crystallization could be suppressed, and room-temperature liquid crystalline phases were obtained. The mesomorphic properties of several mixtures of ionic liquid crystals were investigated. Many mixtures showed full miscibility and ideal mixing behavior; however, in some instances we observed, surprisingly, complete demixing of the component SmA phases. The ionic liquid crystals and mixtures presented have potential applications, due to their low melting temperatures, wide temperature ranges, and stability with extra ion-doping.     

Mechanism of metallization of ionic crystals by pressure

Experimental data on the compressibility of the high-pressure phases of a number of ionic crystals were used to calculate the energies of compression corresponding to the energies of atomization of these substances. It was found that interatomic distances in the compressed substances are equal to the sum of radius of the metal cation and the covalent radius of the nonmetal atom. The mechanism of the metallization of ionic crystals, in particular, the sources of delocalized electrons, was discussed.     

Lattice energy estimation for inorganic ionic crystals

An empirical method based on chemical bond theory for the estimation of the lattice energy for ionic crystals has been proposed. The lattice energy contributions have been partitioned into bond dependent terms. For an individual bond, the lattice energy contribution made by it has been separated into ionic and covalent parts. Our calculated values of lattice energies agree well with available experimental and theoretical values for diverse ionic crystals. This method, which requires detailed crystallographic information and elaborate computation, might be extended and possibly yield further insights with respect to bond properties of materials.     

Defect-assisted conductivity in organic ionic plastic crystals

In order to determine the role of defects (vacancies and extended lattice defects) in the conductivity mechanism of a well studied organic ionic plastic crystal electrolyte, conductivity and mean defect volumes were measured. The ionic conductivity of the salt showed a characteristic phase dependence. Defect volumes, as measured by positron annihilation lifetime spectroscopy, showed increasing rates of expansion with increasing rotational disorder. The dependence of ionic conductivity on defect volume was observed to be phase dependent. Increases in mean defect volume size below approximately 100 cm(3) mol(-1) did not always facilitate ionic conductivity. It was shown that the material undergoes a solid-solid phase transition to the most disordered phase (a plastic crystalline phase with the highest conductivity) when the mean defect volume becomes larger than the molar volume of either the rotating anionic or cationic species. Conductivity in this phase had the strongest dependence on defect volume. Critical volumes calculated from the free volume model of Cohen and Turnbull were unrealistically large.     

Polymerised ionic liquid crystals bearing imidazolium and bipyridinium groups

Novel kinds of polymerised ionic liquid crystals (PILCs) bearing imidazolium and bipyridinium groups were synthesised and characterised in this work. Some bromo-polyesters were synthesised in an esterification chain reaction using 2,3-dibromosuccinyl dichloride, isophthaloyl chloride and 4,4′-biphenol. The polyester imidazolium bromides (PIBs) and polyester dipyridinium bromides (PDBs) were obtained by a quaternisation reaction between the bromo-polyesters, N-methylimidazole and 4-4′-bipyridine, respectively. The polyester imidazolium tetrafluoroborates (PITs) and polyester dipyridinium tetrafluoroborates (PDTs) were synthesised using the corresponding PIBs and PDBs in an anion-exchange reaction. The chemical structures, liquid crystalline properties and molecular weights of these polymers were characterised by multiple experimental techniques. All the PILCs including PIBs, PDBs, PITs and PDTs display smectic A phase on heating and cooling cycles. The liquid-crystalline properties of bromo-polyesters are influenced by the length of flexible spacer and composition of polyester backbones, while those of PILCs are determined by the ionic groups as additional important influent factors. In comparison with those of the mother bromo-polyesters, the d-spacing of PILCs reduced slightly due to Im⁺–Br^?, Dp⁺–Br^?, Im⁺–BF₄^? and Dp⁺–BF₄^? ion pairs in the polymer systems. Monocationic imidazolium salts display weaker interionic and intermolecular interaction, higher mobility and lower viscosity than dicationic dipyridinium salts.     

Cluster models of ionic crystals: Band gaps

We performed electronic ab initio calculations of ion clusters simulating a piece of ionic crystal. Our main interest here is to estimate the (direct) energy band gap from the cluster energy levels. The model consists of a central cation surrounded by four shells of ions, with additional point charges embedding the cluster. We present results for the series of alkali halides with rock-salt structure. © 1996 John Wiley & Sons, Inc.