Appearance of nonuniform electric fields in solid ionic conductors

A computer model is used to study charge transport in ionic materials upon the application of an electrochemical potential gradient. The model incorporates both the diffusion and drift mechanisms, permitting the evaluation of the contribution of each mechanism. Each mechanism is shown to be dominant depending on the material parameters and the experimental conditions. The results obtained are compatible with experimental and theoretical ones as reported in the literature, suggesting that in several cases studying the transport of mobile species in ionic materials upon the application of an electrochemical potential gradient, the existence of an internal field cannot be ignored. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 4, pp. 398–401. The text was submitted by the authors in English.     

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.     

Electric field-derived point charges to mimic the electrostatics in molecular crystals

Because of the way the electrostatic potential is defined in a crystal, it is not possible to determine potential-derived charges for atoms in a crystal. To overcome this limitation, we present a novel method for determining atomic charges for a molecule in a crystal based on a fit to the electric field at points on a surface around the molecule. Examples of fits to the electric field at points on a Hirshfeld surface, using crystal Hartree-Fock electron densities computed with a DZP basis set are presented for several organic molecular crystals. The field-derived charges for common functional groups are transferable, and reflect chemical functionality as well as the subtle effects of intermolecular interactions. The charges also yield an excellent approximation to the electric field surrounding a molecule in a crystal for use in cluster calculations on molecules in solids.     

Synthesis and characterisation of imidazolium-based ionic liquid crystals bearing a cholesteryl mesogenic group

A series of cholesteryl-containing imidazolium chlorides and imidazolium tetrachloroaluminates were synthesised, and the chemical structure, liquid crystalline behaviour and ionic conductivity were characterised by several technical methods. Whereas the imidazolium chlorides show chiral smectic A (SmA*) phase on heating and cooling cycles, the imidazolium tetrachloroaluminates display chiral nematic (N*) phase, which is uncommon for ionic liquid crystals (ILCs). The imidazolium chlorides display similar phase transition temperature and entropy, indicating the cholesteryl component influence predominately on the phase transition rather than the different alkyl substituent groups. The imidazolium tetrachloroaluminates show lower melting point temperatures and lower clear point temperature than the imidazolium chlorides. The mesophases exist at rather moderate temperatures. Non-mesomorphic imidazolium tetrachloroaluminate(III) salts with short alkyl substituents have been known for a long time, and the synthesised imidazolium tetrachloroaluminates are the first examples of tetrahalogenoaluminate(III)-containing ILCs. For the imidazolium tetrachloroaluminates, imidazolium cations combine loosely with AlCl₄^? ions because AlCl₄^? ions are large and occupy more space in spite of the hydrogen bond and electrostatic attraction interaction, indicating that the layer structure can be destroyed easily to form N* phase on heating.     

Effects of alkyl chain length on properties of 1-alkyl-3-methylimidazolium fluorohydrogenate ionic liquid crystals

A series of 1‐alkyl‐3‐methylimidazolium fluorohydrogenate salts (C_xMIm(FH)₂F, x=8, 10, 12, 14, 16, and 18) have been characterized by thermal analysis, polarized optical microscopy, IR spectroscopy, X‐ray diffraction, and anisotropic ionic conductivity measurements. Liquid crystalline mesophases with a smectic A interdigitated bilayer structure are observed from C₁₀ to C₁₈, showing a fan‐like or focal conic texture. The temperature range of the mesophase increases with the increase in the alkyl chain length (from 10.1 °C for C₁₀MIm(FH)₂F to 123.1 °C for C₁₈MIm(FH)₂F). The distance between the two layers in the smectic structure gradually increases with increasing alkyl chain length and decreases with increasing temperature. Conductivity parallel to the smectic layers is around 10 mS cm^?1 regardless of the alkyl chain length, whereas that perpendicular to the smectic layers decreases with increasing alkyl chain length because of the thicker insulating sheet with the longer alkyl chain.     

Anion driven ionic liquid crystals: The effect of the connecting group in [closo-1-CB9H10]- derivatives on mesogenic properties

Replacement of the connecting CH₂ group in ionic liquid crystal 1a[Pyr] with an oxygen atom in 1b[Pyr] resulted in significant destabilisation of the nematic and, to a greater extent, smectic A (SmA) phases, as established from binary mixture studies in 2a[Pyr]. Density functional theory (DFT) modelling of both anions suggests that the destabilisation results from the difference in charge distribution rather than conformational changes. Binary mixture studies demonstrated that all three ionic liquid crystals are compatible with a non-ionic benzoate nematic host 3a.     

T-shaped ionic liquid crystals based on the imidazolium motif: exploring substitution of the C-2 imidazolium carbon atom

In this contribution the first examples of so‐called rigid‐core, T‐shaped imidazolium ionic liquid crystals, in which the C‐2 atom of the imidazolium ring is substituted with an aryl moiety decorated with one or two alkoxy chains, are described. The length of the alkoxy chain(s) was varied from six to eighteen carbon atoms (n=6, 10, 14–18). Whereas the compounds with one long alkoxy chain display only smectic A phases, the salts containing two alkoxy chains exhibit smectic A, multicontinuous cubic, as well as hexagonal columnar phases, as evidenced by polarising optical microscopy, differential scanning calorimetry, and powder X‐ray diffraction. Structural models are proposed for the self‐assembly of the molecules within the mesophases. The imidazolium head groups and the iodide counterions were found to adopt a peculiar orientation in the central part of the columns of the hexagonal columnar phases. The enantiotropic cubic phase shown by the 1,3‐dimethyl‐2‐[3,4‐bis(pentadecyloxy)phenyl]imidazolium iodide salt has a multicontinuous Pm$\bar 3In this contribution the first examples of so-called rigid-core, T-shaped imidazolium ionic liquid crystals, in which the C-2 atom of the imidazolium ring is substituted with an aryl moiety decorated with one or two alkoxy chains, are described. The length of the alkoxy chain(s) was varied from six to eighteen carbon atoms (n=6, 10, 14-18). Whereas the compounds with one long alkoxy chain display only smectic A phases, the salts containing two alkoxy chains exhibit smectic A, multicontinuous cubic, as well as hexagonal columnar phases, as evidenced by polarising optical microscopy, differential scanning calorimetry, and powder X-ray diffraction. Structural models are proposed for the self-assembly of the molecules within the mesophases. The imidazolium head groups and the iodide counterions were found to adopt a peculiar orientation in the central part of the columns of the hexagonal columnar phases. The enantiotropic cubic phase shown by the 1,3-dimethyl-2-[3,4-bis(pentadecyloxy)phenyl]imidazolium iodide salt has a multicontinuous Pm ?3m structure. To the best of our knowledge, this is the first example of a thermotropic cubic mesophase of this symmetry.     

Discotic ionic liquid crystals of triphenylene as dispersants for orienting single-walled carbon nanotubes

Orient and conduct: Triphenylene-based discotic ionic liquid crystals (ILCs) with six imidazolium ion pendants can disperse pristine single-walled carbon nanotubes (SWNTs). When the ILC is columnarly assembled, doping with SWNTs results in macroscopic homeotropic columnar orientation. Combination of shear and annealing treatments gives rise to three different orientation states, which determine the anisotropy of electrical conduction.     

Interaction of water molecules with the electric field of an ionic-crystal surface

A theoretical investigation of the coulombic interaction of water molecules with an ideal surface of an ionic crystal is conducted. The calculation is based on the Fourier transform of the long-range part of an coulombic potential with subsequent summation of its Fourier images and tabulation of the results. The method is numerically tested when solving the problem concerning the interaction with the surface of a silver iodide crystal. A comparison of the electric field near an ideal crystalline surface and its finite fragment is performed. The data obtained point to a strong dependence of electrochemical properties of the surface on the presence of crystalline defects on it.     

To the question on radiationless transitions in electronically excited zones of molecular crystals

A model is proposed describing the dynamics of radiationless transitions in the energy zones corresponding to excited electronic states in molecular crystals. In this model, the migration effect is explicitly reflected, which initially appears under pulse excitation of the systems with a periodical structure of a density distribution of states in separate parts of molecular crystals.     

Nanocomposites of ferroelectric liquid crystals and FeCo nanoparticles: towards a magnetic response via the application of a small electric field

ABSTRACT

We study a nanocomposite consisting of a ferroelectric liquid crystal and a magnetic nanoparticle in order to explore the possibility of using it as a magnetic resonant imaging contrast agent which will measure a field of 20 V/m. To achieve this we use the ferroic properties exhibited by the nanocomposite. We used the ferroelectric liquid crystal 2-(4-((2-fluorooctyl)oxy)phenyl)-5-(octyloxy)pyrimidine mixed with FeCo nanoparticles nominally 2–3 nm in diameter in concentrations of 0.56, 4.3 and 10.8 wt%. The 10.8 wt% sample was chosen for our study because the nanoparticles acted as a lubricant for the ferroelectric liquid crystal. This concentration yields nanoparticle clusters in about 5 ? 10 μm diameter spherulites. An electric field as low as 5V/cm is enough to turn and realign the spherulites where the particles are contained. We estimate the value of the magnetic in a spehrulite and associate it to the number of spherulites aligned as a function of electric field. We find thus that we can achieve low electric fields.     

Periodic electro-optical characteristics of ion-doped Smectic A phase liquid crystals driven by a low-frequency electric field

Functional liquid crystal (LC)-based electro-optical materials are promising candidates in a wide range of smart fields due to their excellent external stimuli-responsive characteristics. Herein, ion-doped Smectic A (SmA)-phase LCs gradually change from a transparent to a scattering state and then return to the transparent state via a circularly driven low-frequency electric field. All optical states can be maintained after removing the electric field. This phenomenon is due to charge transport and convection effects that appear and disappear periodically in SmA LCs doped with suitable ionic liquids. Diverse periodic characteristics were observed upon applying electric fields with different waveforms (e.g. square, sawtooth, and sine). Furthermore, the optical contrast of the periodic feature was abated by increasing the frequency of the electric field. These ion-doped SmA LCs can be widely used in multi-stable optical devices, optical switches, and timers, etc.     

Progress on the optoelectronic functional organic crystals

Organic crystals constructed by pi-conjugated molecules have been paid great attention to in the field of organic optoelectronic materials. The superiorities of these organic crystal materials, such as high thermal stability, highly ordered structure, and high carrier mobility over the amorphous thin film ma-terials, make them attractive candidates for optoelectronic devices. Single crystal with definite struc-ture provides a model to investigate the basic interactions between the molecules (supramolecular interaction), and the relationship between molecular stacking modes and optoelectronic performance (luminescence and carrier mobility). Through modulating molecular arrangement in organic crystal, the luminescence efficiency of organic crystal has exceeded 80% and carrier mobility has been up to the level of 10 cm2·V?1·s?1. Amplified stimulated emission phenomena have been observed in many crys-tals. In this paper, we will emphatically introduce the progress in optoelectronic functional organic crystals and some correlative principle.     

Comparative studies of static dipole polarizabilities of ionic crystals on the basis of different self-consistent potentials

The static dipole polarizabilities, ^D , have been studied for the ions O^2–, F^–, Na⁺, Mg²⁺, Cl^–, K⁺ and Ca²⁺ in the crystals NaF, KF, NaCl, KC1, MgO and CaO. The starting zero-order wave functions have been generated using various exchange- and exchange-correlation potentials in order to study the effect of these potentials on ^D . The direct contribution to the dipole polarizability, _o ^D , has been determined by the uncoupled Hartree-Fock method. Self-consistency effects have been included by the geometric approximation. The crystal potential is incorporated using the Watson sphere model. Good agreement between theoretical and experimental results are found for those self-consistent potentials which exclude self-interaction.     

Colloidal single crystals of silica spheres in the presence of simple- and poly-electrolytes,and ionic detergents

Colloidal single crystals of silica spheres (103 nm in diameter) are formed in the presence of various kinds of salts 1 simple electrolytes, i.e., sodium chloride, calcium chloride and lanthanum chloride, 2 polyelectrolytes such as 3–6 type ionen polymer (polybrene), poly-N-ethylpyridinium bromide, a copolymer ofN-benzyl pyridinium chloride andN-hexadecyl pyridinium bromide, and sodium polyethylene sulfonate, and 3 cationic and anionic detergents, hexadecyltrimethylammonium bromide and sodium dodecylsulfate. Shape and size of their single crystals, phase diagram, and the relationship between the two parameters among the critical concentration of melting, conductance and pH of the crystal-like suspensions have been studied. Colloidal single crystals ofpositively charged spheres have been formed in this study by the method of the charge reversal of spheres through the strong adsorption of cationic polyelectrolytes onto the anionic silica spheres.     

Sulfur makes the difference: synthesis and mesomorphic properties of novel thioether-functionalized imidazolium ionic liquid crystals

Novel thioether-linked imidazolium ionic liquid crystals were synthesized starting from methyl 2-mercaptoacetate. The mesomorphic properties were determined by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction. All mesogens displayed smectic A mesophase geometries with strongly interdigitated bilayer structures. Comparison of the thioether-linked imidazolium salts with the corresponding amine- and amide-linked imidazolium salts as well as simple N-alkyl-imidazolium salts showed that both mesophase width and stability increased with increasing softness of the linking unit, thus indicating the beneficial effect of sulfur. Additionally, an increase of the length of the linking unit decreased the interdigitation of the alkyl chains.