From monomeric to polymeric ferroelectric liquid crystals A comparative study of ferroelectric properties

Two new ferroelectric oligosiloxanes, a cyclic tetramer and a twin, have been synthesized. By a comparative study with their corresponding monomer and side chain polysiloxanes, the influence of oligo- and polymerization on the liquid crystalline and ferroelectric properties have been investigated. Polymerization leads to a stabilization of LC phases through increase of the clearing temperatures and suppression of crystallization. Oligomerization also leads to mesophase broadening, but, due to the low degree of polymerization, the effect is inferior to the linear polysiloxanes. The low viscosity of the oligosiloxanes ensures response times in the microsecond region, thus being comparable with their monomer and conventional LMWFLCs. It is found that polymerization increases the spontaneous polarization P_s. This is attributed to the density increase after polymerization, enhancing the inter-mesogenic interactions. The collective and local dynamics of the OFLCs are influenced differently with respect to their molecular structures. Each oligomer is already a good model for its corresponding polymer concerning the soft mode dynamics. For the local β-relaxation a similar temperature dependence of the relaxation times τ for the cyclic tetramer and for the side chain polysiloxanes is observed. The long axial rotation of the twin, having a very efficient decoupling, is significantly faster, thus resembling the monomer.     

S=N versus S+-N-: an experimental and theoretical charge density study

To elucidate the bonding situation in the widely discussed hypervalent sulfur nitrogen species, the charge density distributions rho(r) and related properties of four representative compounds, methyl(diimido)sulfinic acid H(NtBu)(2)SMe (1), methylene-bis(triimido)sulfonic acid H(2)C[S(NtBu)(2) (NHtBu)](2) (2), sulfurdiimide S(NtBu)(2) (3), and sulfurtriimide S(NtBu)(3) (4), were determined experimentally by high-resolution low-temperature X-ray diffraction experiments (T = 100 K). This set of molecules represents an ideal frame of reference for the comparison of SN bonding modes, because they contain short formal S=N double bonds as well as long S-N single bonds, some of them influenced by inter- or intramolecular hydrogen bonds. For comparison, the gas-phase ab initio calculations of the four model compounds, H(NMe)(2)SMe, H(2)C[S(NMe)(2)(NHMe)](2), S(NMe)(2), and S(NMe)(3), were performed. The topological features were found to be not particularly sensitive with respect to different substituents R (R = H, Me, tBu). In this paper, it is documented that theory and experiment differ in the eigenvalues of the Hessian matrix because of systematically differing positions of the bond critical points but agree very well concerning the spatial Laplacian distribution and the distinct polarization of all investigated sulfur-nitrogen bonds. Both recommend the S(+)-N(-) formulation of sulfur nitrogen bonds in 1 and 2 since all nitrogen atoms are found to be sp(3) hybridized. The planar SNx (x = 2, 3) units in the diimide 3 and the triimide 4 reveal characteristics of m-center-n-electron systems. For none of the investigated S-N bonds, a classical double bond formulation can be supported. This is further substantiated by the NBO/NRT approach. Valence expansion to more than eight electrons at the sulfur atom can definitely be excluded to explain the bonding.     

Permittivity and AC conductivity in yttria-stabilized zirconia

Alternating current (ac) conductivity and permittivity measurements were carried out on yttriastabilized cubic zirconia, with yttria varying from 9.6 to 25.5 mol%. In this composition range, the dielectric constant measured at 10³ Hz decreased from 29.8 to 23.2 as the yttria concentration increased. A plot of the ac conductivity versus frequency exhibited a plateau conductivity (_dc) and a frequency () dependent term '(). An analysis of '() with a suitable theoretical approach based on a pairs-approximation model, resulted in a calculated binding energy for the yttrium-associated oxygen vacancy of 0.29±0.05 eV, which compares favorably with values obtained by different means in previous studies. The experimental determination of the frequency dependence of the conductivity and its analysis provides an effective basis for understanding the ionic conductivity mechanism.     

Separation and identification of non-steroidal antirheumatic drugs containing a free carboxyl function using high-performance liquid chromatography

Different methods for the separation and identification of eighteen non-steroidal antirheumatics (non-steroidal, anti-inflammatory drugs) and the application of these methods for systematic toxicological analysis are reviewed. A method for separating these compounds by high-performance liquid chromatography using an RP-18 column and mixtures of acetonitrile and acetate buffers as eluents is presented and the detectability of these substances with respect to their different UV maxima is discussed.     

Zur Chemie des Chlorisocyanates 3. Mitt.: 1,3-Dichloruretidindion,ein neues Dimeres von Chlorisocyanat

Zusammenfassung Es werden die Eigenschaften und Reaktionen von 1,3-Dichloruretidindion, einem neuen Dimeren des Chlorisocyanats, beschrieben. Durch thermische Isomerisierung entsteht der bereits bekannte N,N-Dichlor-N-carbonylharnstoff. Die IR-Spektren beider Verbindungen werden mitgeteilt.

---

Chemistry of chloro-isocyanate, III: 1,3-Dichlorouretidinedione, a new chloroisocyanate dimer

The properties and reactions of 1,3-dichloro-uretidinedione, a new dimer of chloro-isocyanate, are described. Its thermic isomerization gives the known N,N-dichloro-N-carbonyl-urea. The IR-spectra of both compounds are published.

---

---

Mit 2 Abbildungen     

Orientation and order in thin films of a combined liquid crystalline polymer

The order in thin films of a combined liquid crystalline polymer is studied by X-ray reflection. Films of thicknesses of less than 200 nm on float glass are investigated as a function of temperature. The polymer with mesogenic groups in the main and side-chains exhibits smectic and cholesteric mesophases. Measurements in the smectic phases show a Bragg peak and smectic layers are oriented parallel to the substrate. The sample is thus macroscopically ordered by the influence of substrate and free surface. The film surface is very smooth after spincoating; surface roughness is typically 0.8 nm. First annealing of samples leads to a significant roughening of the free surface; roughness increases to 2.1 nm. Order as a function of film thickness depends on the interaction of the polymer with the substrate and free surface. These interactions give rise to a typical correlation length of perturbations in smectic ordering.     

Si-E (E = N, O, F) bonding in a hexacoordinated silicon complex: new facts from experimental and theoretical charge density studies

The concept of hypervalency in molecules, which hold more than eight valence electrons at the central atom, still is a topic of constant debate. There is general interest in silicon compounds with more than four substituents at the central silicon atom. The dispute, whether this silicon is hypervalent or highly coordinated, is enlightened by the first experimental charge density determination and subsequent topological analysis of three different highly polar Si-E (E = N, O, F) bonds in a hexacoordinated compound. The experiment reveals predominantly ionic bonding and much less covalent contribution than commonly anticipated. For comparison gas-phase ab initio calculations were performed on this compound. The results of the theoretical calculations underline the findings of the experiment.