The mesophases of octa-alkanoyloxy-9,10-anthraquinone

Nine members of the octa-n-alkanoyloxy-9,10-anthraquinone series, ranging from octanoyloxy (n = 8) to hexadecanoyloxy (n = 16) (where n is the number of carbon atoms per chain), were prepared and their mesomorphic properties studied by differential scanning calorimetry and optical microscopy. All the compounds studied are mesomorphic with the higher homologues exhibiting two (for n ≧ 12) or even three (for n ≧ 14) columnar mesophases. For n = 8 to 11, the phase sequence is C-D_B-I, where D_B is an optically biaxial mesophase with a two-dimensional pgg symmetry. For n = 12, 13, the phase sequence is C-M₃-D_B-I, where M₃ is a highly ordered phase whose structure has not been identified. Finally for n = 14 to 16, the phase sequence is C-M₃-D_B-D_A-I, where D_A is an hexagonal phase. In all cases, the phases change from high to low order with increasing temperature and all transitions are first order. Compared with the corresponding hexa-substituted naphthoquinones the present series generates larger mesomorphic ranges and the higher homologues exhibit a uniaxial phase which is lacking in the hexa-substituted series. The increase in volume occupied by the aliphatic chains in the octa-substituted series is evidently sufficient to reduce the interaction between the aromatic cores of the different columns to permit the stability of a uniaxial phase.     

High speed parallel synthesis of banana-shaped molecules and phase transition behaviour of 4-bromo-substituted derivatives

Novel derivative series of the well known bent-shaped P-n-O-PIMB liquid crystal mesogens, referred to as ‘4Br-P-n-O-PIMB’, ‘4Cl-P-n-O-PIMB’ and ‘5Cl-P-n-O-PIMB’, having halogen atoms substituted on the phenyl ring in the central core, were synthesized by solution phase parallel synthesis based on a combinatorial approach. The mesomorphic behaviour and physical properties of all the new compounds were studied by means of optical microscopy, differential scanning calorimetry, X-ray and circular dichroism spectroscopy. We found interesting transitional behaviour for the 4Br-P-n-O-PIMB homologous series. The homologues with alkyl tails having carbon numbers of n=3–10, 12, 14 exhibit rather complicated mesomorphic behaviour, which is strongly sensitive to n. The chiral fluid smectic B2 phase with SmC_AP_A structure and unidentified smectic Bx phase were observed in the homologues with n=9, 10, 12, 14 and n=3–5, respectively. Interestingly, every member exhibits frustrated and/or helical ordered phases at low temperatures, designated as X1, X2, and X3 phases, which result from a spontaneous escape from a macroscopic polarization. The mesomorphic behaviour and mesophase structures differ remarkably from those of the parent P-n-O-PIMB homologues, suggesting that substitution of the halogen atoms at the central core essentially creates a particular interaction between molecules.     

The N,N'-bis[4-(4-n-alkyloxybenzoyloxy)benzylidene]phenylene-1,3-diamines: mesophase behaviour and physical properties

A homologous series of banana-shaped compounds (n =1-12) is described. The short-chain derivatives exhibit a B₆ phase, while B₆/B₁ dimorphism is found for the pentyloxy and hexyloxy homologues. The B₁ phase of the compounds having longer alkyloxy chains is changed to a B₂ phase for the compounds with n =11 and 12. The phase characterization was performed using their optical textures and by means of X-ray investigations. Transition enthalpies were measured using DSC. In addition, density measurements were performed on one selected homologue. The compound n =8 exhibiting a B₁ phase was investigated also by high-pressure DTA.     

Dual switchable six-ring bent-core liquid crystals with azo linkages exhibiting B1 and B2 mesophases

A new series of asymmetric bent-core compounds were synthesised using azo linkages with equal as well as unequal terminal alkyl chains and their photo and electrical switching properties investigated. The mesomorphic properties were characterised using polarised optical microscopy, X-ray diffraction and differential scanning calorimetry. The lower homologues of the series of compounds show a B₁ phase whereas higher homologues exhibit a B₂ phase. The B₂ phase shows an anticlinic-antiferroelectric switching behaviour during electro-optic measurements. The photo-switching properties of the azobenzene containing bent-core molecules were investigated using ultraviolet-visible spectroscopy. The trans to cis photo isomerisation was observed at 25 s whereas reverse processes took 14 h in chloroform.     

Phase-transition studies of 5O.5 and 9O.4

As part of our detailed comparative studies of groups of liquid-crystalline compounds that belong to a homologous series, we present phase-transition studies of the compounds N-(4-n-pentyloxybenzylidene)4′-n-pentylaniline (5O.5) and N-(4-n-nonyloxybenzylidene)4′-n-butylaniline (9O.4) using different experimental techniques. The compound 5O.5 is reported to exhibit a phase sequence N, S_A, S_C, S_B and S_G, while 90.4 shows the sequence S_A, S_F and S_G. The salient features of our work on 5O.5 are (i) a new smectic F phase is found in place of the reported smectic B phase, which is confirmed by both miscibility and X-ray studies; (ii) the formation of smectic-C-like short-range order in the nematic phase well above the S_A-N transition; and (iii) a large tilt-angle variation in the smectic C phase (0–23·5°C) in a small temperature range (4·1°C). The phase changes across the S_A-I transition, and for the first time across S_F-S_A transition, are carried out by volumetric studies. The detailed inferences of these are also presented.     

Calamitic liquid crystals of 1,2,3-triazole connected to azobenzene: synthesis,characterisation and anisotropic properties

Azobenzene-based calamitic liquid crystals, 4-((4-(4-methoxymethyl-1,2,3-triazol-1-yl)phenyl)diazenyl)phenylalkanoates have been isolated and their structures were characterised. The structure–property correlation with respect to the different alkanoyloxy terminal chain (–COOC_nH_2n+1 where n adopts odd numbers ranging from 3 to 15) has also been given attention in the present study. In this series, all compounds exhibit smectogenic properties. The lower homologues shows enantiotropic SmA phase as well as monotropic SmC phase. The higher homologues exhibit homeotropic alignment of smectic phases. These compounds possess very high anisotropic inclination in which the mesomorphic region covers nearly 80°C.     

Synthesis and mesomorphic properties of banana-shaped compounds derived from 2,7-dihydroxynaphthalene

Thirty eight compounds composed of achiral banana-shaped molecules belonging to three new homologous series have been synthesized and their mesomorphic properties investigated. The mesophases have been characterized using a combination of polarized light microscopy, differential scanning calorimetry, miscibility methods and X-ray diffraction measurements. All the compounds reported exhibit mesomorphic properties. Most of the homologues in the three series show B₁ and B₂ phases and the transition temperatures of these are lower in the fluoro substituted compounds. Some of the lower homologues of the fluoro substituted derivatives also show the nematic phase.     

Occurrence of the B 7 mesophase in two homologous series of seven-ring achiral compounds composed of banana-shaped molecules

The synthesis and mesomorphic behaviour of twenty compounds belonging to two new series of seven-ring esters derived from 2-cyanoresorcinol are reported. Many homologues of both series exhibit the B₇ mesophase. In addition, some of the lower homologues exhibit a mesophase which shows textural features similar to that of the two-dimensional B₁ phase. The characterization of the mesophases has been carried out using polarizing optical microscopy, differential scanning calorimetry, X-ray diffraction, miscibility studies and electro-optical investigations. The first example of a plot of the B₇-isotropic phase transition temperature as a function of the alkyl chain length is also reported.     

Biaxial phase and coexistence of the two uniaxial nematic phases in the system sodium dodecyl sulphate–decanol–D2O

The system sodium dodecyl sulphate (SDS)/decanol (DeOH)/water presents, with temperature increase, an unusual phase transition between a stable biaxial phase and a coexistence region of the two uniaxial nematic phases (discotic N_D + cylindrical N_C). This has been detected previously by several methods for a sample with water/SDS molar ratio M_w = 36. Here, this system is investigated changing the ratio M_w to 32, where previously the coexistence region was reported after a discotic N_D phase, without the biaxial phase. We report now the existence of a biaxial N_B in the temperature range of ~2°C, defining for both values of M_w and the phase sequence as N_B – (N_D + N_C) – N_C. The change in temperature is followed by conoscopic and orthoscopic optical techniques and also analysed through the curve obtained by the technique of digital image processing of the textures, which reveals a continuous transition N_D – N_B – (N_D + N_C). While the biaxial phase is stable for at least 10 hours, in a reproducible way, the coexistence region evolves with time, and drops of the discotic phase grow immersed in a N_C matrix. Results are explained in terms of recent theories dealing with stabilisation of mixtures of cylinders and discs.     

Electro-optical investigations and effect of asymmetry in bent-core liquid crystals

We report the synthesis and mesomorphic properties of a homologous series (10a–10g) of bent-core molecules constructed through covalent linkage of structurally non-symmetrical rod-like mesogens connected with a 1, 3-phenylene unit. The study of homologous series underlines the importance of length and nature of terminal chains. The homologues of shorter chains show a typical non-switchable rectangular columnar B₁ phase, while the switchable lamellar (B₂) phase is induced on moving to higher homologues. X-ray diffraction patterns indicate the presence of B₁ and B₂ mesophases. Polarised optical microscopy investigations under electric field in the B₂ phases revealed the existence of anticlinic antiferroelectric texture. The measured spontaneous polarisation value in one of the compounds is 936 nC cm^?2, a high polarisation value in bent-core liquid crystals.     

Liquid crystalline properties and photochromism of N-[4-(4-n-alkoxybenzoyloxy)-2-hydroxybenzylidene]-methoxy and -ethoxy anilines

New homologous series of N-[4-(4-n-alkoxybenzoyloxy)-2-hydroxybenzylidene]-methoxy and -ethoxyanilines were synthesized. The phase transitions of these homologues were determined using differential scanning calorimetry and an polarizing microscopy: para-substituted homologues exhibit a nematic phase, while ortho-substituted members do show no mesomorphic phase. In addition, some members of these homologous series exhibit a photochromic property in the solid state.     

The influence of terminal chlorine on the mesomorphic properties of new thiobenzoates containing two and three benzene rings

New liquid crystalline chloro‐substituted thioesters containing two and three benzene rings have been synthesized. 4‐Chlorophenyl 4‐n‐alkoxythiobenzoates and 4‐chlorophenyl 4‐n‐alkoxybenzoyloxy‐4′‐thiobenzoates are referred to as nO.SCl and nO.OSCl, respectively, where n varies from 4 to 16 for nO.SCl, from 4 to 10 for nO.OSCl and denotes the number of carbon atoms in the alkyl chain. Their mesomorphic properties were investigated by means of polarizing optical microscopy, differential scanning calorimetry, transmittance light intensity and X‐ray diffraction measurements. The nO.SCl homologous series possesses smectic A (SmA) and nematic (N) phases for n?=?4, 5, 6 while higher homologues have only an enantiotropic SmA phase. Those from the nO.OSCl homologous series have enantiotropic N and SmA phases and higher transition temperatures. The range of the N phase decreases, and of the SmA increases, with the elongation of the alkoxy chain in the nO.OSCl homologous series. The effect on mesomorphic behaviour of terminal alkoxy chain lengthening and replacement by chlorine on the other side of the molecule is discussed.     

The synthesis and liquid crystalline behaviour of 2-(4-n-alkoxyphenyl)-5-methylpyridines

We have synthesized a new series of polyphenylene compounds with a pyridine ring, 2-(4-n-alkoxyphenyl)-5-methylpyridines (CH₃C₅H₃NC₆H₄OC _i H_2i1) (1a-i ; the carbon number, i, of the alkoxy group is 1-9), and studied their phase transitions and mesogenicity using DSC and polarizing microscopy. In the homologous series of 1a-i , no mesomorphic phase appeared for i=1-5 and only a monotropic nematic phase was observed for i=6-9. The mesomorphic potential is relatively weaker for the 1a-i than for the 2a-i and 3a-i homologues, which are pyridine-containing three- and four-ring similar systems. This lowering of the mesogenicity may be due to the lack of a phenyl ring between the pyridine ring and the methyl group in the 1a-i homologues.     

The effect of locations of triple bond at terphenyl skeleton on the properties of isothiocyanate liquid crystals

Three series of new tolanyl benzene isothiocyanate liquid crystals A, B and C were synthesised with lateral fluorine substituent at different positions and 3,5-difluoro terminal groups. Series D and compound E4 with carbon–carbon triple bond connected with the isothiocyanated benzene were also prepared as reference. Their structures were confirmed using infrared spectrometry, nuclear magnetic resonance and mass spectrometry. The mesomorphic properties, birefringence, dielectric anisotropy and miscibility of these compounds were investigated. Series A exhibits higher clearing points than that of the corresponding compounds D. Series B displays the lowest melting points, the broadest nematic phase temperature range and no smectic phase with increase of the carbon number of alkyl chain. Lateral fluorine in the position of Y (series C) results in an increase of smectic phase. The birefringence (~0.454–0.490) of series A is almost the same as that of the corresponding reference compounds D, while series B shows a decrease of Δn about 0.05 compared with compounds D. For comparison, mixtures formulated by A and B exhibit higher clearing points and better low temperature stability than those of the mixtures based compounds D in the same fraction.     

Mesomorphic phase transitions of tetraphenylporphyrins with four long aliphatic chains

Abstract

Studies of 5,10,15,20-tetrakis(4-n-alkylphenyl)porphyrins revealed that the homologues with longer alkyl chains than hexyl were mesomorphic, in contrast to the non-mesomorphic alkoxy derivatives. Metal complexes (Co, Ni, Cu, Zn, and Pd) of the dodecyl derivative were also shown to exhibit mesophases. These mesophases were assigned as discotic lamellar (D_L) phases by X-ray diffraction studies.     

Columnar liquid crystals in oligosaccharide derivatives. II. Two types of discotic columnar liquid-crystalline phase of cellobiose alkanoates

Abstract

A series of cellobiose octaalkanoates, Cel-II-n (n is the carbon number of the alkyl chain), with n = 7–14 were prepared and their mesogenic properties examined by differential scanning calorimetry, optical polarizing microscopy and X-ray diffraction. All of these compounds form enantiotropic discotic columnar phases, in which the columns are built up by a regular stacking of the cellobiose moieties and are packed in a two dimensional lattice. Homologues with n = 9–14 form the D_ho phase only whilst the compound with n = 7 forms the D_ro phase. The n = 8 compound forms the D_ho phase at higher temperatures and the D_ro phase at lower temperatures. Structural parameters obtained from X-ray diffraction studies are presented for both phases.     

Synthesis of new schiff base ester liquid crystals with a benzothiazole core

A series of new calamitic liquid crystals, 6-methoxy-2-(4-alkanoyloxybenzylidenamino)benzothiazoles, comprising a benzothiazole core, terminal methoxy group and a Schiff base linkage were synthesised and characterised. This series comprises 12 members wherein members differ by the length of the alkanoyloxy chain (C _n-1H_2n-1COO-, where n?=?2–8, 10, 12, 14, 16, 18). Their mesomorphic properties were studied by using differential scanning calorimetry, optical polarising microscopy and powder X-ray diffraction techniques. The short chain derivatives (n?=?2 and 3) were non-mesogenic compounds, while an enantiotropic nematic phase was present throughout the remaining members of the series. The smectic C phase emerged from the decanoyloxy derivative onwards.     

Approximation of any physicochemical constants of homologues with the use of recurrect functions

Dependencies of various physicochemical constants of organic compounds (A) versus number of carbon atoms in the molecule within different homologous series [A = f(n _C )] usually are non-linear. The simplest recurrent equation A(n + 1) = a A(n) + b, connecting A-values for homologues (n + 1 carbon atoms) with the values of the same constants for previous members of series (n carbon atoms), indicates practically “ideal” linear character for most properties of organic compounds. It is the reasonable basis for approximation (or extrapolation) any physicochemical constants within any homologous series using the standard approach without special selection of appropriate algebraic functions. Principal mathematical properties of the function A(n + 1) = aA(n) + b and some of its chemical applications are considered.     

A study of homologation and the occurrence of an SA-SC-SA sequence of phases in the 4-n-alkoxy-3-fluorophenyl 4-(5-n-alkyl-2-thienyl)benzoates

Abstract

Seventeen esters, derived from 4-n-alkoxy-3-fluorophenols and 4-(5-n-alkyl-2-thienyl)benzoic acids, have been prepared and their liquid crystal transition temperatures determined by thermal optical microscopy. On cooling the isotropic liquid, the S_A-S_C-S_A sequence of phases reported for the octyloxy-octyl and octyloxy-nonyl esters has been observed for certain other homologues, principally members of the 4-(5-n-nonyl-2-thienyl)benzoates. For these compounds, the temperature range of occurrence of the intermediate S_C phase decreases as the length of the alkoxy chain increases (for the hexyloxy-nonyl to dodecyloxy-nonyl esters) and the S_c phase is absent for the tetradecyloxy-nonyl homologue.     

Phase transition behaviours of calamitic liquid crystals comprising phenylbenzothiazole core

A series of new calamitic liquid crystals 2-[4-(4-alkyloxybenzoyloxy)-phenyl]benzothiazoles comprising a benzothiazole core, terminal alkyl chain and an ester linkage were synthesised and characterised. This series consists of 13 members, wherein the members differ by the length of alkyloxy chain (C _n H_2n+1O^?, where n?=?2–10, 12, 14, 16, 18). Their mesomorphic properties were studied by using differential scanning calorimetry, optical polarising microscopy and powder X-ray diffraction techniques. Enantiotropic nematic phase was present throughout the series, i.e. from the lowest member (n?=?2) until the highest member (n?=?18) of the series. The smectic A phase emerged from the nonyloxy derivative onwards.