Conoscopic image of a biaxial nematic phase in a sodium decyl sulfate – decanol – D2O mixture

ABSTRACT

The nematic phases of a lyotropic system NadS/ decanol/ heavy water are investigated using optical conoscopy and image processing. The phase diagram obtained from these lyotropic materials predicts the occurrence of a direct phase transition, which does not present the biaxial nematic phase, between the discotic (N_D) and calamitic (N_C) nematic phases. A biaxial nematic (N_B) phase is optically characterized and confirmed through conoscopic image, inside the biaxial range, between the two uniaxial nematic phases. Also, their respective transition points are determined by means of image processing. The N_B phase observed here is discussed as part of the nature of the micellar configuration of lyotropic materials which exhibit uniaxial nematic phases.     

Nematic States in Micellar Systems of Mixed Composition

The correlation between the molecular composition of micelles and the temperature stability of micellar nematic states is investigated on mixtures of cetyltrimethylammonium bromide (CTAB) or decyltrimethylammonium bromide (DTAB) with decylammoniumchloride (DACl) or potassium laurate (KL), 1-decanol, and NaBr. The phases were identified using a polarizing microscope. Replacing, in a CTAB/l-decanol system with a nematic phase, CTAB mole by mole with KL increases the temperature stability of the lamellar smectic state but the width of the nematic range is reduced. Similarly, replacing CTAB with decanol increases the stability of the smectic state and reduces the width of the nematic range. In contrast, replacement of CTAB by DACl has little effect on the width of the nematic range up to 35% replacement and no enhancement of the temperature stability of a latent smectic state is observed. The results are qualitatively interpreted in terms of the electrostatic interactions of the ionic surfactants and of the surface areas per headgroup.     

An optical microscopy study of the biaxial ‐ calamitic nematic lyotropic phase transition

Lyotropic nematic textures are investigated, using optical microscopy, near the reentrant isotropic (I_RE) ‐ discotic nematic (N_D^‐) ‐ biaxial nematic (N_B) ‐ calamitic nematic (N_C⁺) ‐ isotropic (I) phase transitions in a lyotropic mixture of potassium laurate, decanol and D₂O. The N_B, intermediate phase between the two uniaxial nematic ones, is characterized by optical birefringence measurements. In this way, using a polarizing microscope and a colour CCD digital camera, the N_B – N_C⁺ phase transition is identified as well as the domain of the N_B phase and N_D^‐ – N_B transition point in accordance with optical birefringence data (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Proton Spin Relaxation in the Rod Micelles of Type I CM Mesophases

The dynamics of the hydrocarbon chains in lyotropic nematic type I cylindrical micellar liquid crystals prepared with D₂O has been selectively studied by Zeeman and rotating frame nuclear spin-lattice relaxation. The measurements of the proton spin-lattice relaxation time T ₁ as a function of frequency and temperature demonstrate that relatively fast local fluctuations of individual amphiphilic chains relax the proton spins at high magnetic fields. This process is facilitated also by the rapid diffusive motion of the chains within the micellar units. The rotating frame Zeeman relaxation time T _1x, is associated at room temperature with a long correlation time of ~11 μs. Slow micellar orientational fluctuations have been assigned to this characteristic time.     

Identification of nematic lymoesophases with discotic and cylindrical micelles in lyotropic amphiphilic systems

Nematic lyomesophases with discotic (N _D) and cylindrical (N _C) micelles in complex multicomponent lyotropic systems based on alkyltrimethylammonium bromide detergents have been identified by the ¹H-²H-, and ¹³C-NMR methods and polarizationoptical microscopy. The difference in the structures of the N _D and N _C nematic phases is especially pronounced in the ¹³C-NMR spectra. Addition of chiral dopants to the lyomixture facilitates formation of the Ch _D and Ch _C cholesteric phases. According to the ¹³C-NMR spectra, the micellar mobility in the cholesteric lyomesophases decreases in comparison with the nematic ones. The alignment of lyocholesterics under the action of an external magnetic field is found.     

Measurements of optical anisotropy of a calamitic lyotropic liquid crystal

Optical birefringence measurements for a calamitic lyotropic liquid crystal containing sodium lauryl sulphate/decanol/water are presented. A value of the order of 10^‐3 was obtained, much smaller than that of thermotropic liquid crystals. The order parameter temperature dependence is evaluated using an extrapolating method and taking into accounts the influence of the micelle shape. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X-ray diffraction study of p-(alkoxybenzylidene)-p′-toluidines: Crystal and molecular structure of C10H21O-C6H4-CH=N-C6H4-CH3

The crystal and molecular structure of p-(decaoxybenzylidene)-p′-toluidine C₁₀H₂₁O-C₆H₄-CH=N-C₆H₄-CH₃ is studied. The molecule is nearly planar. In the crystal packing, loose regions formed by aliphatic fragments of molecules alternate with pseudostacks of aromatic fragments of molecules that are related by the centers of symmetry. The stacks are built of dimers, in which molecules are linked by π-stacking interactions between benzene rings. There are no weak directional interactions between dimers in a stack. The presence of a single structure-forming element in the crystal, namely, the π-stacking interactions in the dimers, along with the similarity of the crystal packing to that of the C₈H₁₇O-homologue, which forms a nematic mesophase on melting, indicate that the crystals under study should exhibit nematic properties.     

Crystal and molecular structure of 4′-hexyloxyphenyl 4-pentylbenzoate

The molecular and crystal structure of 4??-hexyloxyphenyl 4-pentylbenzoate, C₆H₁₃O-C₆H₄-COO-C₆H₄-C₅H₁₁, which is a liquid-crystal compound, was determined by X-ray diffraction. This compound forms a nematic phase upon melting. The crystal contains three crystallographically independent molecules. In one of them, the alkyl chain is disordered. This is indicative of the looseness of the crystal packing in the aliphatic region. The crystal structure is stabilized by the following two types of weak directional interactions: hydrogen bonds with the participation of the terminal O atom of the ester group and the C-H group of one of the benzene rings and C-H????-system interactions. Only one of the three independent molecules is involved in the latter type of interactions. Hence, the structurization of the mesophase is most likely determined by hydrogen bonding.     

Molecular and crystal structure of liquid crystalline p-octyloxyphenyl p′-pentyloxybenzoate

The crystal and molecular structure of p-octyloxyphenyl p′-pentyloxybenzoate C₅H₁₁-O-C₆H₄-C(O)-O-C₆H₄-O-C₈H₁₇, which forms a nematic mesophase upon melting, was determined by X-ray diffraction. There is one system of weak directional intermolecular C-H…π interactions responsible for the formation of the nematic phase in these crystals.     

Viscoelastic Parameters of a Side-Chain Nematic Polymer: I—Results of a Proton NMR Study

The reorientational behaviour in a static magnetic field of a nematic siloxane side-chain polymer is investigated by proton NMR. At variance with what occurs in main-chain and lyotropic nematic polymers, the return to equilibrium of a tnonodomain whose mean director has been rotated at an angle α to the field, is found to be homogeneous for all angles a between 0 and π/2. The usual nematic order parameter and the static (on the proton NMR time scale) order parameter are deduced from analysis of the equilibrium lineshapes. The twist viscosity γ₁ is deduced from the study of time dependent lineshapes following the rotations α. The temperature dependence of γ₁ is discussed in terms of the Vogel equation γ₁ = B S ^β exp(E _β/R(T - T _o}). It is not possible to discriminate between β = 1 or 2, but in both cases, the freezing temperature of the director T_o is found to be non-zero. A nematic to smectic pretransitional effect on γ₁ is observed. The information concerning the viscoelastic parameters contained in the value of the static order parameter is also discussed.     

Study of deviation from normal liquid crystal behavior of mesomorphic-isotropic transition curve in a chalconyl ester series with equipolar terminal end groups

A novel chalconyl ester homologous series RO.C₆H₄.COO.C₆H₄.CO-CH:CH-C₆H₄.OC₈H₁₇(p) synthesized and studied with a view to understanding and establishing the relation between molecular structure and Liquid Crystal (LC) properties of thermotropic mesomorphs. The novel series consists of eleven homologous (C₁ to C₁₆). Enantiotropicnematic type of mesophase formation commences from C₃ homologue and continued up to the last C₁₆ homologue of a novel series. Smectogenic character is totally absent for the novel series. Transition temperatures and the textures of nematic phase were determined through an optical polarizing microscopy (POM) equipped with a heating stage. Textures of nematic phase are threaded or Schlieren. Transition curve Cr-N/I and N-I behaved in normal manner except C₈ homologue which showed negligible deviation from normal behavior. N-I transition curve exhibited odd–even effect. Analytical and structural data supported the molecular structures of homologues. Average thermal stability for nematic is 98.88°C whose degree of mesomorphismvary from 12.0°C to 37.0°C. Evaluated thermometric data of present novel series are compared with structurally similar series. Group efficiency order for nematic on the basis of thermal stability, early commencement of mesophase and the degree of mesomorphism. Thus, present series is predominantly nematogenic and lower middle ordered melting type the low degree of mesomorphism.     

Redetermination of the crystal structure of [Na4(H2O)14]SnS4: a compound containing a novel chain of aquated sodium ions

[Na₄(H₂O)₁₄]SnS₄ is obtained by the reaction of Na₂S·9H₂O with SnCl₄·5H₂O in aqueous solution at 21°C. It crystallizes in the space group Cc with a = 8.621(2) Å, b = 23.543(5) Å, c = 11.358(2) Å, = 110.58(3)° and V = 2158.2 ų with Z = 2. Refinement of 3826 unique reflections from a racemically twinned crystal yielded a final value of R₁ = 0.0464 (|F| > 4) and wR₂ = 0.104 and a goodness of fit of 1.125. The structure consists of a Na⁺/H₂O network supporting the tetrahedral SnS₄ ^4– anions. Water molecules or sulfide ions octahedrally coordinate each of the four crystallographically independent Na⁺ ions. The dominant feature of the structure is the existence of zigzag chains of edgeshared Na octahedra. These chains are tied together into a three-dimensional network by bridging Na(H₂O)₆ octahedra and individual H₂O molecules.     

Molecular and crystal structure of 4-hexylbenzoic acid: Design of the mesophase

The crystal structure of 4-hexylbenzoic acid C₆H₁₃-C₆H₄-COOH, which forms a nematic mesophase upon melting, is determined. The crystal contains three crystallographically independent molecules. Their molecular skeletons are made up of two almost planar fragments: a benzene ring, π-conjugated with the carboxyl group and a planar zigzag aliphatic fragment. One of the independent molecules forms centrosymmetric dimers via pairs of hydrogen bonds between carboxyl groups, whereas the two others are linked via hydrogen bonds. The dimers in the crystal are packed into pseudostacks with a pronounced nonparallel arrangement of conjugated fragments. There is no good mutual projecting of benzene rings in the stacks, which corresponds to efficient π-stacking interaction. The graph describing the mesophase of this compound contains only one structure-forming element (a hydrogen bond) and corresponds to the nematic mesophase.     

Synthesis and structural characterization of dihexamethylenetetraminetetraaquocobalt(II) hexaaquocobalt(II) sulfate hexahydrate

The synthesis and crystal structure of a new three dimensional cobalt(II) complex [Co(C₆H₁₂N₄)₂(H₂O)₄Co(H₂O)₆][SO₄]₂.6H₂O are reported. It crystallizes in the triclinic space group P-1 with a = 13.394(3), b = 16.077(3), c = 9.282(2) Å, = 89.71(2), = 90.42(2), = 114.02(2)°, V = 1825.6(7)ų and Z = 2. The structure is comprised of [Co(C₆H₁₂N₄)₂ (H₂O)₄Co(H₂O)₆][SO₄]₂ units and H₂O molecules. Two molecules of ligand and four molecules of water chelate one type of Co^II in an octahedral fashion through two N and four O atoms: the four O atoms form the equatorial plane and the two N atoms occupy the apical positions. The other type of Co^II cation is chelated by six water molecules.     

Crystal and molecular structure of n-hexyloxyphenyl n-octyloxybenzoate

The X-ray crystal structure of n-hexyloxyphenyl n-octyloxybenzoate C₈H₁₇O-C₆H₄-COO-C₆H₄-OC₆H₁₃, which is a liquid-crystal compound, was determined. This compound forms smectic and nematic phases upon melting. A crystal-packing analysis revealed the following two types of structure-forming elements in the centrosymmetric pairs of molecules: a ??-stacking interaction and a C-H...??-system interaction. In the pairs of molecules linked by the latter type of interactions, there are two such interactions per pair, whereas one interaction occurs per pair of molecules linked by a ??-stacking interaction. Hence, the former pair of molecules is more stabilized through weak directional interactions than the latter pair.     

Synthesis, crystal structure, and thermal analyses of triaqua-(1,10-phenanthroline-N,N′) succinatomanganese(II) dihydrate, [Mn(H2O)3(phen)(C4H4O4)]·2H2O

[Mn(H₂O)₃(phen)(C₄H₄O₄)]·2H₂O was obtained by reaction of freshly prepared MnCO₃, phen and succinic acid in CH₃OH/H₂O (1:1 v/v), and its crystal structure has been determined by single crystal X-ray diffraction methods. The title mixed ligand complex crystallizes in the triclinic space group with cell dimensions a = 7.590(1) Å, b = 9.324(1) Å, c = 13.917(1) Å, = 85.64(1)°, = 74.56(1)°, = 77.10(1)°, and D _calc = 1.584 g/cm³ for Z = 2. The crystal structure consists of the [Mn(H₂O)₃(phen)(C₄H₄O₄)] complex molecules and lattice H₂O molecules. The Mn atoms are each octahedrally coordinated by two N atoms of one phen ligand and four O atoms of three H₂O molecules and one succinato ligand with d(Mn—N) = 2.271 and 2.299 Å, and d(Mn—O) = 2.133–2.239 Å. Through intermolecular hydrogen bondings, the complex molecules are interlinked to form 2D layers, which are assembled by – stacking interactions into 3D framework with tunnels occupied by the lattice H₂O molecules. Thermal analyses showed that the title compound decomposes in two steps over the range 25–600°C upon heating in flowing Ar.     

Dependence of mesomorphism on geometrical shapes of isomeric and nonisomeric series of chalconyl esters

A meta substituted chalconyl ester homologous series: RO?C₆H₄?COO?C₆H₄(meta)?CO?CH?CH?C₆H₄?OC₁₂H_25(n)(para) is synthesized and studied with a view to understanding the effect of molecular substitution at meta position in a molecular structure on thermotropic liquid crystal properties. The novel homologous series consists of thirteen homologues (C₁ to C₁₈). All the homologues except the nonliquid crystal homologues C₁, C₂, C₃ are enantiotropic nematic with the absence of smectic properties. The transition and melting temperatures were determined by an optical polarizing microscopy (POM) equipped with a heating stage. Textures of a nematic phase are threaded or Schlieren. Transition curves (Cr-N/I and N-I) behave in normal manner except homologues between C₁₀ and C₁₄ of N-I curve, which show negligible deviation from normal and a smooth descending tendency. The N-I transition curve exhibits an odd-even effect up to C₁₀ homologue and then the odd-even effect disappears for higher homologues. Analytical and the spectral data support the molecular structures. Thermal stability for nematic is 107.3°C and the mesophase lengths range between 13.0°C and 35.0°C at the C₁₈ and C₁₂ homologues respectively. Group efficiency order for nematic is derived on the basis of thermal stability as ?OC₁₂H_25(n) (linear) > ?OC₁₂H_25(n) (nonlinear) > ?OC₁₆H₃₃ (nonlinear).     

Study of mesomorphism dependence on molecular flexibility of an azoester series containing a napthyl unit

A novel azoester homologous series of liquid crystalline (LC) compounds: RO?C₆H₄-COO?C₁₀H₆-N:N-C₆H₄?OC₄H₉(n) without lateral substitution has been synthesized and studied with a view to understanding and establishing the effects of molecular structure on thermotropic LC substances with reference to tailed-end group. The novel homologous series consists of 13 homologs (C₁ to C₁₈) whose nematogenic and smectogenic mesomorphism commences enantiotropically from C₆ and C₁₂ members of the series, respectively. The C₁₂–C₁₈ homologs are smectogenic and C₆–C₁₈ are nematogenic, of which C₁₂–C₁₈ homologs are smectogenic plus nematogenic. The C₁–C₅ homologs are nonmesogenic. Transition temperatures and the textures of the homologs were determined and identified by an optical polarizing microscope (POM) equipped with a heating stage. Textures of a nematic phase are threaded or Schlieren and that of the smectic phase are of the type A or C. Transition curves Cr-M/I, Sm-N and N-I of a phase diagram behaved in normal manner except N-I transition temperature of C₁₀ homolog which deviated by 9°C–10°C from normal behavior. N-I transition curve exhibited odd-even effect. Analytical, spectral, and thermal data confirms the molecular structures of homologs. Thermal stability for smectic and nematic are 115.5°C and 138.5°C, respectively whose corresponding mesophaselengths are varied from 10.0°C to 16.0°C and 13.0°C to 24.0°C, respectively. Group efficiency order for smectic and nematic are derived from comparative study of structurally similar analogous series; as smectic: ?OC₄H₉ (n) > ?CH₃ > ?H; Nematic: ?H > ?OC₄H₉ (n) > ?CH₃     

Crystal structure of a seven-coordinate cobalt(II) complex with a new polyfunctional hydrazonic ligand, [Co(H4dapis)(OH2)2]Cl2·9/2H2O

A seven-coordinate cobalt(II) complex has been synthesized with a new hydrazonic ligand, H₄dapis, and its crystal structure determined by X-ray diffraction methods and refined toR 0.0564 for 2763 independent reflections. The structure consists of [Co(H₄dapis)(OH₂)2] cations, Cl anions, and lattice H₂O molecules interlinked by hydrogen bonds. The cobalt atom has a distorted pentagonal bipyramidal environment with two axial H₂O molecules and the H₄dapis ligand forming the basal plane.