Mesomorphic properties of liquid crystalline compounds with chalconyl central linkage in two phenyl rings

In order to investigate the influence of the central linking group and the effect of flexibility on mesomorphism, we have synthesised a newly homologous series 3-(3-butoxyphenyl)-1-(4-n-alkoxy phenyl) prop-2-en-1-one (series-l) consisting of 13 homologues C₁–C₈, C₁₀, C₁₂, C₁₄, C₁₆ and C₁₈. In the present series, mesophase commences from the C₆ homologue. C₁–C₅ homologues did not exhibit liquid crystalline (LC) property, while C₆–C₁₂ homologues exhibited an enantiotropic nematic phase and the rest of the homologues C₁₄–C₁₈ displayed monotropic SmC and nematic mesophase. The transition temperatures of the synthesised compounds were determined by an optical polarising microscopy equipped with a heating stage. All newly synthesised compounds were confirmed by ¹H-NMR, ¹³C-NMR, IR and elemental analysis.     

X-ray diffraction study of mesophase bitemplate-containing silicas

The effect of the composition of a bitemplate (solubilization) mixture on the formation of a spatially organized structure of mesophase siliceous systems has been investigated by X-ray diffraction. Alkylpyridinium halides (C _n PyHal with n = 8?16 (counterion Cl) and 18 (counterion Br)) were used a solubilizator, and monoethanolamides (EAC _m ) of saturated n-aliphatic acids (m = 10?16) and trialkylphosphine oxides (H_{2e + 1}C _e )₃PO, where e = 8, 10, or 12, were used as solubilizates. Differences in the mesophase structure of template-containing silicas synthesized in aqueous and aqueous salt (NaCl) solutions have been revealed. It is shown that the type and degree of ordering of the silica mesophase structure depends on the nature, spatial organization, and the solubilizator and solubilizate concentrations.     

Control of the Discotic to Isotropic Transition in Alkoxy-Substituted Silicondihydroxo-Phthalocyanines by Axial Substituents

The synthesis of a homologous series of octaalkoxy-substituted silicondihydroxo-phthalocyanines is described. The mesomorphic properties of these new materials were studied by DSC, optical microscopy and X-ray investigations. Compounds with n ≤ 4 (n is the number of carbon atoms in a single alkoxy side chain) show a discotic mesophase transition. A transition to the isotropic state is only observed when n ≤ 8. X-ray diffraction patterns of the mesophases confirm that all compounds form a hexagonal columnar mesophase of the type D_hd.     

Mesophase design: I. Molecular structure and crystal packing motifs of 4-alkylcyanobiphenyls

A comparative study of the crystal and molecular structures of 4-alkylcyanobiphenyls (ACB-n) C _n H_{2n + 1}-C₆H₄-C₆H₄-CN (n = 2, 4–12) belonging to liquid-crystal compounds revealed no direct relationship between the molecular geometry of these compounds and their liquid-crystalline properties. Mesogenic properties are determined by the alternation of the loosely packed aliphatic and closely packed aromatic regions in the crystals. Graphs describing the crystals and mesophases were designed for ACB-n. The graph for nematic mesogens of ACB-n (n = 5−7) has one structure-forming element. The graph for smectic-nematic (n = 8 and 9) and smectic (n = 10−12) mesogens have more than one structure-forming element. If different types of secondary bonds in the smectic mesophase have equal energies, the disruption of these interactions caused by the temperature rise occurs simultaneously and the system undergoes a transition from the smectic phase to the isotropic liquid. If the energies of different types of secondary bonds are different, the destruction of the mesophase occurs in steps and the phase transitions are more complicated (smectic-nematic-isotropic transitions).     

Refractive index and dispersion measurements in prismatic thin film of phasmidic columnar liquid crystals

In this work, we explore the refractive index of the phasmidic columnar liquid crystal for homeotropic oriented samples (column perpendicular to the plates). To measure the ordinary index n_o of the columnar liquid crystal C₁₀, a simple and accurate method is presented using the deflection by reflection of a laser beam (λ = 633nm) through a prismatic phasmidic thin film placed between two glass plates in the homeotropic orientation. For the C₁₀ samples, we found n_o = 1.5512 ± 0.0002 at T = 100°C. We used the same method to determine the isotropic index n_l of the isotropic phase and found n_l = 1.5301 ± 0.0002 at T = 120°C. Using the precision of the same method in polychromatic laser beam, we measured the variation of the ordinary index with the wavelength λ and characterize the dispersion by the known Cauchy's dispersion relationship n_o = A + B/λ². We deduce an estimation of the birefringence for several samples.     

Imidazolium based ionic liquid crystals: structure,photophysical and thermal behaviour of [Cnmim]Br·xH2O (n = 12, 14; x=0, 1)

The long chain imidazolium halides [C_nmim]Br·xH₂O (n = 10, 12; x = 0, 1) have been synthesized and their structural and thermal behaviour together with their photophysical properties characterized. X‐ray structure analyses of the monohydrates ([C₁₂mim]Br·H₂O: triclinic, P1, no. 2, Z = 2, Pearson code aP112, a = 550.0(5) pm, b = 779.4(5) pm, c = 2296.1(5) pm, α = 81.89(5)°, β = 83.76(5)°, γ = 78.102(5)°, 3523 unique reflections with I_o > 2σ(I_o), R₁ = 0.0263, wR₂ = 0.0652, GooF = 1.037, T = 263(2) K; [C₁₄mim]Br•H₂O: triclinic, P1, no. 2, Z = 12, Pearson code aP11, a = 549.86(8) pm, 782.09(13) pm, c = 2511.3(4) pm, α = 94.86(2)°, β = 94.39(2)°, γ = 101.83(2)°, 2063 unique reflections with I_o > 2σ(I_o), R₁ = 0.0429, wR₂ = 0.0690, GooF = 0.770, T = 293(2) K) show for both compounds similar bilayered structures. Sheets composed of hydrophilic structure regions constituted by positively charged imidazolium head groups, bromide anions and hydrogen bonded water alternate with hydrophobic areas formed by interdigitated long alkyl chains belonging to imidazolium cations with different orientation. Combined differential scanning calorimetry and polarizing optical microscopy shows that the monohydrates as well as the anhydrous imidazolium salts are thermotropic liquid crystals which adopt smectic mesophases. The mesophase region is larger in case of the monohydrates when compared to the anhydrous compounds indicating that water obviously stabilizes the mesophase. All compounds show an intense whitish photoluminescence with short lived (¹π←¹π*) and long lived (¹π←³π*) transitions. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mesophase design: II. Molecular structure and crystal packing of 4-alkyloxycyanobiphenyls

A joint analysis of the molecular geometry and crystal packings of the members of a homologous series of 4-alkyloxycyanobiphenyl C _n H_{2n + 1}-O-C₆H₄-C₆H₄-CN with n = 5–12 does not reveal a direct relationship between the molecular geometry and mesogenic properties of these compounds. The crystal packings of all of them are built from alternating loose aliphatic and dense aromatic regions. The closely packed aromatic regions of crystals exhibit weak intermolecular directed interactions of different natures which are responsible for the occurrence of the mesophase. The type of mesophase depends on the number s of structure-forming elements, the ratio of their energies (if s > 1), and the melting temperature of the compound. A graph system is used to describe the crystal packings and the mesophase. It is shown that, although the mesophase graph is similar to the crystal graph, they may differ somewhat, because some symmetric limitations (for example, lattice) on the molecular associate structure are removed in the melt.     

New chiral liquid crystal materials based on menthol: Synthesis and phase behavior

To study structure-mesomorphism relationships of chiral materials based on menthol, a series of chiral compounds containing menthyl group were synthesized. Their chemical structures, formula, and the purity were characterized by Fourier transform infrared (FTIR), proton nuclear magnetic resonance (¹H NMR), and elemental analyses. The corresponding phase behavior was investigated with differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The effect of the mesogenic core, flexible spacer, and terminal groups on the mesophase formation and type was discussed. The compound 4-menthyloxyacetoxybenzoyloxy-4′- (6-bromohexyloxy)biphenyl showed the smectic A (S_A) and cholesteric phases on heating cycle, and a cubic Blue Phase, chiral smectic C (S_C^*), S_A and cholesteric phases on cooling cycle. However, the compound 4-menthyloxyacetoxybenzoyloxy-4′-(4-bromobutoxy)biphenyl showed enantiotropic S_C^*, S_A and cholesteric phases, moreover, the platelet texture of a cubic Blue Phase was also observed on cooling cycle. The methacrylate monomer with six flexible methylene units and three phenyl rings as mesogenic core only showed cholesteric phase, while the methacrylate monomer with four methylene unit and three phenyl rings showed the S_C^* and cholesteric phases. However, when the terminal methacryloyloxy groups in the monomers were substituted by thiophenylacryloyloxy groups, the corresponding monomers all show no mesophase. With increasing the rigidity of mesogenic core or decreasing the flexible methylene spacer length, the corresponding melting temperature (T_m) or isotropic temperature (T_i) increased.     

Mesomorphic and DFT studies of terminal ester containing salicylaldimines and their copper (II) complexes

In this article, we report synthesis and characterization of a novel homologous series of butyl 4-(4′-(alkoxy)-2-hydroxybenzylideneamino)benzoates, C_nLH (n = 6, 8, 10, 12, 14, 16) and their copper(II) complexes. The mesomorphic properties of these compounds were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and powder X-ray diffraction (XRD) studies. The ligands and their copper(II) complexes exhibit wide range of enantiotropic smectic A mesophase as confirmed by their typical optical texture under polarizing microscope. Thermal stability of the compounds is determined by thermo gravimetric analyses. DFT calculations have been performed using GAUSSIAN-09 program at B3LYP level to obtain the stable electronic structure of the ligand and its copper(II) complex.     

Role of n-alkoxy terminal end groups on mesomorphism

A homologous series RO-C₆H₄-CH:CH-COO-C₆H₄-CO-CH:CH-C₆H₄-OC₆H₁₃ (n) of novel liquid crystals (LC) has been synthesized and studied with a view to understanding and establishing the relation between molecular structure of a substance and the LC properties or behavior of thermotropic LC materials. Novel series consist of 11 homologues. C₁ and C₂ homologue derivatives are non-LCs and the rest of homologues (C₃ to C₁₆) are nematogenic without exhibition of smectic property. Transition temperatures were determined by an optical polarizing microscopy equipped with a heating stage. Transition curve Cr-N/I of a phase diagram behaved in normal manner. N/I transition curve partly deviated at C₆ and C₁₀ homologues from normal descending behavior, and exhibited very narrow and sharp odd-even effects. Textures of nematic phase are threaded or Schlieren. Thermal, analytical, and spectral data confirmed the molecular structures of novel chalconyl ester derivatives. Thermal stability for nematic is 95.77°C and the upper and lower mesophase lengths vary from 35 to 16°C at C₅ and C₈ homologues respectively. Group efficiency order derived for nematic on the basis thermal stability is -OC₁₀H₂₁ (n) > -OC₈H₁₇(n) > -OC₆H₁₃(n).     

Crystal and molecular structure studies of tris(2-hydroxy-3-t-butyl-5-methylbenzene)-methane trihydrate and N-benzyl-N-phenyl benzamide

The structures of the title compounds, tris(2-hydroxy-3-t-butyl-5-methylbenzene)-methane)C₃₄H₄₆O₃.3H₂O, 3) and N-benzyl-N-phenylbenzamide (C₂₀H₁₇NO, 6), have been investigated by X-ray crystallography. Compound 3 crystallizes in the trigonal space group with cell parameters a = 14.090(5) Å, b = 14.090(5)Å, c = 10.485(5)Å, Z = 2. Compound 6 crystallizes in the monoclinic space group C2/c with cell parameters a = 24.533(4)Å, b = 9.176(4)Å, c = 16.711(5)Å, = 125.88(2)°, Z = 8. Compound 3 has both intra-and intermolecular hydrogen bonds. It also exhibits a helical columnar arrangement of the molecules and goes into mesophase before melting into an isotropic liquid.     

Synthesis and study of mesomorphic properties in rod-like chalconyl compounds

In order to investigate the influence of the central linking group and effect on flexibility on mesophase behavior of liquid crystal we have synthesized newly homologous series viz. 3-(4-Octyloxyphenyl)-1-(4′-n-alkoxy phenyl) prop-2-en-1-one (Series-l) consists of thirteen homologues (C₁ to C₈, C₁₀, C₁₂, C₁₄, C₁₆, C₁₈). Textures of a nematic phases are threaded or Schlieren type. The textures of smectic and nematic phase are directly judged from the heating and cooling condition. Group efficiency order for mesophases is derived on the basis of thermal stabilities from the comparative study of thermometric data determined from structurally analogous series. A transition curve as depicted in a phase diagram behaves in normal manner. Structural and conformational characterization of these new compounds had achieved by ¹H NMR, ¹³C NMR, IR, and elemental analysis.     

X-ray diffraction investigation of two mesomorphic copper(II) complexes of tetra-4-[(4-alkoxycarbonyl)phenyleneoxy]phthalocyanine

The mesomorphism and supramolecular structure of two homologues of copper tetra-4-[(4-alkoxycarbonyl)phenyleneoxyl]phthalocyanines are investigated using optical polarizing microscopy, differential scanning calorimetry (DSC), and X-ray diffraction. It is revealed that both homologues, which contain four and nine carbon atoms in aliphatic fragments of the lateral substituents, exhibit thermotropic columnar mesomorphism with a hexagonal arrangement of ordered columns (Col _ho). A change in the length of the aliphatic fragment has no noticeable effect on the mesophase type and leads only to variations in the parameters of the hexagonal lattice formed by the columns. The glass transition temperature of the homologue with n = 4 (T _g = 88°C) is considerably lower than that of the homologue with n = 9 (T _g = 88°C). It is established that the introduction of the cyclic fragment into the lateral substituent substantially affects the type of column packing as compared to the copper tetra-4-[(n-alkoxy)carbonyl]phthalocyanines studied in our earlier works. The assumption is made that this difference is associated, in particular, with the specific features of the penetration of the lateral substituents of the adjacent columns either in the presence or in the absence of the cyclic fragment in the lateral substituent.     

A Novel Polyoxometalate-Based Hybrid Materials Composed of Octamolybdate and Hexamuclear Copper Cluster Units

Self-assemble of aqueous solution of the Cu²⁺/molybdate/glyc-ine system results in {[NaCu₆(Gly)₈(H₂O)₂][Mo₈O₂₆Cu(Gly)₂]₂}_n·n{NaCu₆(Gly)₈(H₂O)₂}·n{Mo₈O₂₆[Cu(Gly)(GlyH)(H₂O)₂]₂} 15nH₂O 1, which exhibits the 0-D + 1-D supramolecular framework and in which the copper atoms show three kinds of coordination models: (1) in quadrilateral geometry, (2) in square-pyramidal geometry, and (3) in distorted octahedral geometry. The space group of the compound is P–1, with the lattice parameters: α = 89.036(5)°, β = 89.384(4)°, γ = 88.337(5) °, a = 12.559(4) Å, b = 14.441 (4)Å, c = 23.063(6) Å, and Z = 1.     

Molecular structural flexibility dependence of mesomorphism through ortho-substituted bromo group

A novel series of liquid crystal (LC) materials of Schiff's bases viz. RO-C₆H₄?CH?CH?COO?C₆H₄?N?CH?C₆H₄?Br (ortho) is synthesized and studied with a views to understanding and establishing the effect of molecular structure on liquid crystal properties and to provide novel thermotropic LC material to the scientific and technological community of research interest. The novel series consists of thirteen members (C₁ to C₈, C₁₀, C₁₂, C₁₄, C₁₆ &; C₁₈). All the members of a series are enantiotropic liquid crystals. Smectic (C₁₀?C₁₈) and nematic (C₁?C₁₈) property commence from C₁₀ and C₁ homologue respectively. Transition temperatures and the textures of homologues were determined using a polarizing optical microscope (POM) equipped with a heating stage. Transition curves Cr-M, Sm-N and N-I of a phase diagram behaved in normal manner. Odd–even effect is absent for Sm-N transition curve, but it is present for N-I curve. Sm-N transition curve is extrapolated to C₈ and C₆ nonsmectogenic homologues to determine and predict their latent ability for exhibition of smectic property. Analytical and spectral data confirms the molecular structures of homologues. Thermal stabilities of smectic and nematic are 85.4°C and 130.1°C °C whose upper and lower total mesophase length vary from 58.0°C to 06.0°C at the C₁₀ and C₁ = C₅ = C₆ homologue, respectively. Textures of nematic phase are threaded or Schlieren and smectic phase are of type A or C. LC properties of present novel series are compared with structurally series known series. Thus, present novel series is predominantly nematogenic and partly smectogenic with middle ordered melting type and considerable total mesophase length range.     

Phase Transitions of Urea Adducts with n-Paraffins under High Pressure

The temperatures of the phase transition between orthorhombic and hexagonal structures of the urea adducts with n-paraffins, n-C_nH_2n+2 (n = 14–44), have been measured by differential thermal analysis for the pressure range up to 250MPa. The transition temperatures increase both with pressure and with the number of carbon atoms of the guest paraffins. The increasing rate of the transition temperatures with pressure is about half of that of pure paraffin crystals. The pressure dependences of the lattice constants have also been measured by X-ray diffraction. The specific volume changes discontinuously at the transition pressure; the result suggests that the phase transition of the urea adducts with n-paraffins is a first-order one. Furthermore, the specific volume change at the transition pressure decreases with the number of carbon atoms of the guest paraffins; 3.4 × 10-⁶ m³/Kg for n = 16 and 2.1 × 10-⁶ m³/Kg for n = 44.     

Modification of the Interlayer in HTiNbO5 and its Physicochemical Characterization

Abstract

A layered titanoniobate, in which the interlayer of the metal oxide based on octahedral framework is pillared with silica, has been prepared from HTiNbO₅ by employing alkylamines (C_nH_2n+1NH₂, n = 4, 6, 8, 10) and tetraethylorthosilicate as interlayer exchange guests and a pillar precursor, respectively. The incorporated amine had bilayer arrangements in the interlayer space and their ammonium head groups pointed to the host (TiNbO5₅ ^?) layers. While the basal spacing of the compounds increased with the chain length of alkylamine. the inclination angle also increased. The intercalated structure facilitated the incorporation of tetraethylorthosilicate into the interlayers, and silica-pillared layered titanoniobate was obtained after calcination. The physicochemical properties of the resultant pillared compounds were characterized on the interlayer microstructure, nitrogen adsorption and UV-VIS absorption spectra.     

Thermoelectric power of indium sesquisulphide single crystals

The investigation covers a temperature range from 200 to 450 K. Thermoelectric power measurements of In₂S₃ crystals showed that all samples under investigation have a positive TEP in all temperature ranges, indicating n-type conductivity for In₂S₃ crystals. The ratio of the electron and hole mobilities is μ_n/μ_p = 4.71. The effective mass of electrons m is found to be 0.00008 × 10⁻³¹ kg. The obtained effective masses of holes m = 1.893 × 10⁻³¹ kg. The diffusion coefficient for both carriers (electrons and holes) is evaluated to be 84.71 cm²/s and 17.985 cm²/s respectively. The mean free time between collision is estimated to be τ_n = 1.7 × 10⁻²⁰s, and τ_p = 8.5 × 10⁻¹⁷s. The estimated diffusion length for electrons is found to be L_n = 1.2 × 10⁻⁹ cm and L_p = 3.9 × 10⁻⁸ cm.     

Tetra-n-butylammonium bromide-thiourea (1/2), a layer-type inclusion compound

The inclusion compound built of tetra-n-butylammonium bromide-thiourea (1/2), [(n-C₄H₉)₄N⁺Br^– 2(NH₂)₂CS], has been prepared and characterized by X-ray crystallography. The compound crystalline in orthorhombic space group Pbca, with a = 16.872(6) Å, b = 17.214(6) Å, c = 18.561(6) Å, V = 5390(3) ų, Z = 8. The compound features a sandwich-like crystal structure built up from planar layers. In the crystal structure, zigzag hydrogen-bonded thiourea ribbons are linked by bromide anions to generate puckered layers matching the (100) planes, and the (n-C₄H₉)₄N⁺ cations occupy the intervening space.     

Cotton-Mouton Effect in Monodisperse Suspensions of Liquid Crystals

Abstract

The collective Cotton-Mouton (C-M) effect in the system of micron-size liquid-crystal droplets freely suspended in the isotropic liquid is studied experimentally and theoretically. The collective C-M constant in liquid-crystal suspensions is found to be from 10⁴ to 10⁸ times higher than the respective “molecular” C-M constant in the isotropic phase of the same substance. These large values cause the saturation in the C-M effect at relatively low magnetic fields. Using the generalized nth order Langevin's functions L, _n the statistical therory is presented for the collective C-M effect in the monodisperse liquid-crystal suspensions. As a result, the induced birefringence is obtained in the form Δn = 1/2(Δn)∞ (3L ₂ – 1), where (Δn)∞ is the induced birefringence at saturation. The collective C-M constant is C _c = CN _s S _g where N ₈ is the number of molecules in the droplet, S ₈ is the orientational order parameter of the long molecular axes in the droplet, and C is the “molecular” C-M constant. The resultant (measured) C-M constant is C ₈ = C(1 + N ₈ S ₈). The relaxation time τ depends on the rotational (Brownian) diffusion constant D and after removing the field B the orientational order parameter of the optical axes of droplets in the suspension S _s = 1/2(3L ₂ – 1) vanishes exponentially as S _s = exp(?6Dt). Hence, the relaxation time τ = (6D)^?1.

The collective C-M effect and its saturation can be used as methods for the analysis of the presence and change of the orientational order within colloidal grains and the derivation of several parameters characterizing the aggregation, self-organization, and morphogenesis processes in multicomponent complex systems.