Thermotropic liquid crystalline behaviour of piperazinium and homopiperazinium alkylsulphates

A series of 1,4-piperazinium di- n -alkyl sulphates was synthesized and compared with an analogous series of 1,5-homopiperazinium di- n -alkyl sulphates. Their thermotropic liquid crystalline behaviour was studied by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. For the piperazinium salts, two ordered smectic phases were established, in which the lateral packing of the molecules within the layers is rectangular or tetragonal. Both phases are characterized by an alternate periodic packing of the positive and negative ionic groups in the polar sublayer, while the lipophilic sublayers of the alkyl chains are in a disordered conformation. Substitution of the piperazinium by the less symmetrical homopiperazinium group disfavours organization within the smectic layer and as a result smectic A phases were obtained.     

Synthesis and study of 4‐(4′‐n‐alkoxybenzoyloxybenzoyl)‐4′′‐n‐butoxyanilides

Thirteen compounds with ester and amide linkages were synthesized and their mesogenic properties evaluated. Methyl to n‐propyl derivatives exhibit nematic phases, n‐butyl to n‐decyl derivatives exhibit smectic and nematic mesophases, whereas n‐dodecyl to n‐octadecyl derivatives exhibit only smectic phases. All the smectic homologues exhibit smectic C phases. Middle members of the homologous series exhibit polymorphism of smectic mesophase. A plot of transition temperatures versus number of carbon atoms in the alkoxy chain reveals an odd–even effect for nematic–isotropic transition temperatures. Nematic–isotropic and smectic–cholesteric thermal stabilities of the prepared compounds (series I) are higher compared to those of previously reported compounds, series A, B and C. The results indicate that a simple reversal of a central linkage has a dramatic effect on the appearance of smectic mesophase in a homologous series. The structures of the synthesized compounds were characterized using elemental analysis, thin‐layer chromatography and spectral data.     

Three ring dioxanes as dopants enhancing the stability of the smectic C phase

Abstract

Searching for compounds which could be useful as modifiers of smectic C mixtures, we have synthesized four homologous series of three ring dioxanes, 2BBD, 5BBD, 2CBD, and 5CBD. Their phase transition temperatures and enthalpies were measured and their liquid crystal phases identified. Compounds belonging to series n-BBD form smectic B_cr phases for shorter alkyl chains, and smectic B_cr and A phases, for longer chains. Compounds belonging to the n-CBD series exhibit the smectic A phase, but those with longer alkyl chains have exclusively smectic B phases and those with short tails have other low temperature, highly ordered smectic phases. The compounds were added to smectic C mixture and it was found that some can be useful as dopants. Compounds with longer alkyl tails in the molecule are more suitable for this purpose; the type of ring in the core is less important.     

Synthesis and mesomorphic properties of some biphenyl-phenyl triesters as potential longitudinal ferroelectrics

Abstract

A homologous series of “fraternal twin” molecules consisting of relatively short and relatively long mesogenic units connected by a flexible spacer group and flexible chains as the terminal groups was synthesized in an attempt to form a non-chiral longitudinal ferroelectric smectic phase. The shorter of the two mesogenic units consisted of a 4-alkyl/alkoxy substituted biphenyl ester; the longer a terbenzoate group. Mesomorphic properties were determined by hot-stage polarizing microscopy and DSC. Several smectic phases were observed as well as nematic phases. Characterization of the smectic phases by microscopic textures is discussed.     

Poly(alkyl itaconates) part v copolymers of Selected mono- and di-alkyl esters

Two series of copolymers have been prepared from esters of itaconic acid. Members of type I were synthesised from co-monomers of di-n-alkyl itaconates while type II were composed of a mono-alkyl ester copolymerized with a di-n-alkyl ester. Reactivity ratios were determined for five different copolymers. Both type I and type II copolymers were characterized by differential scanning calorimetry and torsional braid analysis. Several molecular relaxation processes were identified in each series, occurring below the glass transition temperature, Tg. The variation of Tg with type I copolymer composition was examined using Barton's modification of the Gibbs-Di Marzio copolymer equation which gave a satisfactory fit to the data.     

A small-angle neutron scattering study of the ethyl (n-octyl) phosphate micelles in water

Summary Mixed-double chain anionic surfactants, barium- and lithium-salts of ethyl(n-octyl) phosphate (EOP), which are asymmetric in the molecular shape, and a series of identical chain di-n-alkyl phosphate lithium salts have been synthezized. The limiting partial molar volume of a PO ₄ ^– group (23.43±0.41 cm³ mol^–1) for use in small-angle neutron scattering analysis was determined by density measurements of a series of identical chain di-n-alkyl phosphate lithium salts. For lithium EOP-D₂O system, a critical micellar concentration (2.3 wt%) was determined by³¹P NMR spectra. The micellar shape and size in the EOP-water binary system has been investigated by using small-angle neutron scattering (SANS) spectra. It has been found that the micelles of barium EOP in water have the shape of a prolate spheroid and aggregation numbers (n) equal to 48 at 23°C and 52 at 50°C. For the lithium EOP-micellar system, it has been found that the minimum micelle with an aggregation numbern=21 is spherical and micellar growth and variation from the spherical to the prolate shape might occur with an increase in concen tration above the CMC.     

Synthesis and mesomorphic properties of some biphenyl-phenyl triesters as potential longitudinal ferroelectrics

A homologous series of “fraternal twin” molecules consisting of relatively short and relatively long mesogenic units connected by a flexible spacer group and flexible chains as the terminal groups was synthesized in an attempt to form a non-chiral longitudinal ferroelectric smectic phase. The shorter of the two mesogenic units consisted of a 4-alkyl/alkoxy substituted biphenyl ester; the longer a terbenzoate group. Mesomorphic properties were determined by hot-stage polarizing microscopy and DSC. Several smectic phases were observed as well as nematic phases. Characterization of the smectic phases by microscopic textures is discussed.     

Effect of composition on the pressure-induced re-entrant cholesteric phase behaviour of mixtures of non-polar cholesteryl n-alkanoates

Abstract

Recently we reported a pressure-induced re-entrant cholesteric phase for ternary systems of non-polar cholesteryl n-alkanoates. In these systems one component contains a shorter n-alkyl chain than the other two. We now show that the former produces a positive excess volume in the smectic phase, which is probably responsible for the pressure-induced re-entrant phase behaviour. The maximum temperature of the cholesteric/smectic A phase boundary is found to decrease drastically with decrease of the n-alkyl chain length of this particular component.     

Glass and subglass transitions in a series of poly(itaconate ester)s with methyl-terminated poly(ethylene oxide) side chains

A series of poly(itaconate ester)s containing methyl-terminated poly(ethylene oxide) side chains with lengths ranging from 1 to 5 ethylene oxide units has been synthesized. Both heat capacity C_p and dynamic mechanical measurements have been carried out on these polymers using differential scanning calorimetry (DSC) and torsional braid analysis (TBA), respectively. The resulting data for this polymer series are discussed, and comparisons are made with work previously published for the corresponding di-n-alkyl itaconate ester polymers where appropriate.     

Influence of the smectic A-nematic transitional order on the formation of the smectic phases of 4-n-hexyloxybenzylidene-4′-n-butyIaniline and 4-n-butyloxybenzylidene-4′-n-octyIaniline from an electrically deformed nematic phase

Abstract

The crucial role of the smectic A-nematic transitional order for the formation of the smectic A, B and G phases from an electrically deformed nematic phase of the liquid crystal 4-n-hexyloxy-benzylidene-4′-n-butylaniline (6O.4) with a typical smectic A-nematic first order transition and the formation of the smectic A and B phases from an electrically deformed nematic phase of the liquid crystal (4-n-butyloxy-benzylidene-4′-n-octylaniline (40.8) with a smectic A-nematic second order transition has been demonstrated. The nematic phase was deformed by an AC voltage of 2U,_th 5U _th and 10U _th, where U _th is the threshold voltage which causes the appearance of the Fréedericksz transition in the homeotropic nematic layer. The smectic textures have been observed on free cooling of the nematic phase or after the use of an oven. The smectic A phase of the liquid crystal 60.4 was observed with the formation of a clear smectic A-nematic phase boundary while the smectic A phase of the liquid crystal 40.8 has been formed from intermediate pretransitional stripes, observed by Cladis and Torza [1]. The homeotropic anchoring of the direction was crucial for the formation of the smectic phases of the liquid crystal 40.8 but not significant for the liquid crystal 60.4.     

Synthesis and properties of new ionic liquid crystals based on para-nitroazobenzene with substitution vinylimidazolium ion group

A new series of ionic liquid crystals (ILCs), 1-(4-(4-nitrophenylazo)phenyloxy) vinyl-3-methyl-1H-imidazol-3-ium bromide salts (C _n , n?=?6, 10) were synthesised. Their chemical structures were determined by ¹H NMR, ¹³C NMR, UV spectroscopy and elemental analysis. The liquid crystalline properties were investigated by differential scanning calorimetry, polarising optical microscopy, and powder X-ray diffraction. These measurements showed that C _n (n?=?6, 10) exhibit smectic liquid crystalline phases with focal-conic fan-shaped textures. The introduction of vinylimidazolium group onto the azobenzene enhances the thermal stability of the smectic state, which play an important role in forming the smectic layer structure.     

Structural study of smectic A phases in homologous series of N-alkylpyridinium alkylsulphates

The mesomorphic properties of 27 homologues of the N-alkylpyridinium alkylsulphate series were studied by X-ray diffraction and dilatometry. All of these compounds exhibit single smectic A phases whose layer spacings are between 0.64 and 0.8 times the molecular length. Polarizing optical microscopy observation shows that these peculiar layer spacings are not due to the tilting of the molecules; a new packing model is proposed to explain the particular structure of these thermotropic ionic liquid crystal phases.     

Pyrrolidinium Ionic Liquid Crystals

N‐Alkyl‐N‐methylpyrrolidinium cations have been used for the design of ionic liquid crystals, including a new type of uranium‐containing metallomesogen. Pyrrolidinium salts with bromide, bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate, thiocyanate, tetrakis(2‐ thenoyltrifluoroacetonato)europate(III) and tetrabromouranyl counteranions were prepared. For the bromide salts and tetrabromouranyl compounds, the chain length of the alkyl group C_nH_2n+1 was varied from eight to twenty carbon atoms (n=8, 10–20). The compounds show rich mesomorphic behaviour: highly ordered smectic phases (the crystal smectic E phase and the uncommon crystal smectic T phase), smectic A phases, and hexagonal columnar phases were observed, depending on chain length and anion. This work gives better insight into the nature and formation of the crystal smectic T phase, and the molecular requirements for the appearance of this highly ordered phase. This uncommon tetragonal mesophase is thoroughly discussed on the basis of detailed powder X‐ray diffraction experiments and in relation to the existing literature. Structural models are proposed for self‐assembly of the molecules within the smectic layers. In addition, the photophysical properties of the compounds containing a metal complex anion were investigated. For the uranium‐containing mesogens, luminescence can be induced by dissolving them in an ionic liquid matrix. The europium‐containing compound shows intense red photoluminescence with high colour purity.     

Liquid crystalline behaviour of hydrogen-bonded complexes of alkoxycinnamic acids with octyloxystilbazole

Hydrogen-bonded liquid crystalline complexes have been obtained through 1:1 (molar ratio) complexation of 4-n-alkoxycinnamic acids (nCNA: n = 4, 8, 10, 12, where n is the number of carbons in the alkyloxy chain) and trans-4-octyloxystilbazole (8Sz). These hydrogen-bonded complexes (nCNA8Sz) form stable mesophases. The mesomorphic range was extended by the mixing of complexes. Hexatic modification of smectic B (SmB_h), smectic C (SmC), smectic A (SmA), and nematic mesophases of these complexes were determined by a combination of X-ray diffraction and polarizing optical microscopy. Transitions between the various smectic phases were deduced from the temperature-dependent layer spacing of nCNA8Sz. The layer spacing of these complexes in the SmB_h and SmA phases gradually increased with increasing alkoxy chain length. The favouring of smectic phases in these complexes is believed to originate from the increment of polarity of the mesogen by intermolecular H-bonding.     

Self‐Assembly of Imidazolium‐Based Rodlike Ionic Liquid Crystals: Transition from Lamellar to Micellar Organization

By using aryl‐amination chemistry, a series of rodlike 1‐phenyl‐1H‐imidazole‐based liquid crystals (LCs) and related imidazolium‐based ionic liquid crystals (ILCs) has been prepared. The number and length of the C‐terminal chains (at the noncharged end of the rodlike core) and the length of the N‐terminal chain (on the imidazolium unit in the ILCs) were modified and the influence of these structural parameters on the mode of self‐assembly in LC phases was investigated by polarizing microscopy, differential scanning calorimetry, and X‐ray diffraction. For the single‐chain imidazole derivatives nematic phases (N) and bilayer SmA₂ phases were found, but upon increasing the number of alkyl chains the LC phases were lost. For the related imidazolium salts LC phases were preserved upon increasing the number and length of the C‐terminal chains and in this series it leads to the phase sequence SmA–columnar (Col)–micellar cubic (Cub_I/Pm3n). Elongation of the N‐terminal chain gives the reversed sequence. Short N‐terminal chains prefer an end‐to‐end packing of the mesogens in which these chains are separated from the C‐terminal chains. Elongation of the N‐terminal chain leads to a mixing of N‐ and C‐terminal chains, which is accompanied by complete intercalation of the aromatic cores. In the smectic phases this gives rise to a transition from bilayer (SmA₂) to monolayer smectic (SmA) phases. For the columnar and cubic phases the segregated end‐to‐end packing leads to core–shell aggregates. In this case, elongation of the N‐terminal chains distorts core–shell formation and removes Cub_I and Col phases in favor of single‐layer SmA phases. Hence, by tailoring the length of the N‐terminal chain, a crossover from taper‐shaped to polycatenar LC tectons was achieved, which provides a powerful tool for control of self‐assembly in ILCs.     

Mean polarizability of molecules and anisotropy of the Lorentz tensor upon a nematic-smectic a phase transition: Their behavior in a homologous series

Experimental values of the mean polarizability of molecules, [`(g)]\bar \gamma , and components of the Lorentz tensor, L <sub>j</sub> , in the nematic and smectic A phases are obtained for a homologous series of n-alkyl-p-(4-ethoxybenzylideneamino)-α-methylcinnamates. Dependences of the [`(g)]\bar \gamma and L _j values on the mesophase temperature, the orientational order parameter S of molecules, and the number n in the homologous series are revealed. The quadratic dependence of [`(g)]\bar \gamma (S) in the nematic and smectic phases is established that is invariant with respect to the nematic-smectic A transition. Polarizability densities of the molecular core and the alkyl chain are found from the monotone decreasing dependence [`(g)]\bar \gamma (n)/v (where v is volume per one molecule) in the smectic phase. The presence (or absence) of the odd-even alternation of L _j (n) in the nematic (smectic) phase is shown. A monotone decrease in the Lorentz tensor anisotropy L with an increase in n is revealed in the smectic phase, and limiting values L _j (n → ∞) are determined.     

Order in poly(N-(10-n-alkyloxycarbonyl-n-decyl)-maleimides)

Wide-angle and small-angle x-ray diffraction patterns of 11 poly(N-(10-n-alkyloxycarbonyl-n-decyl)maleimides) (PEMI) (including only even members of the series) have been obtained on unoriented samples. They show major maxima at two diffraction angles. The one at the larger angles is due to the interaction of neighboring n-alkyl side-chains. The smaller one (which shows second and third orders of diffraction in higher members of the series, n = 14 to n = 22, where n is the number of methylene groups in the external n-alkyl sequence in the side chain) is related to the distance between lamellar planes formed by the main chains. In all cases, the measured layer separation d_i is higher than the structural unit length L of the side-chain in the most extended conformation, and lower than the length corresponding to two side-chains. On the basis of the experimental results reported here, a model is proposed for the packing of these comblike polymers in the solid state. The mode of packing is also supported by infrared spectra in the 720 cm^?1 region for the ? CH₂? rocking mode of vibration of the n-alkyl side-chain.     

Supercooled Smectic Phases of p-n-Alkoxycinnamoyloxy-p′-Cyanoazobenzenes in Gas–Liquid Chromatography

The sorption properties of supercooled smectic phases of homologues of the p-n-alkoxycinnamoyloxy-p-cyanoazobenzene series were studied by gas–liquid chromatography. Based on the system of universal retention indices, mesomorphic stationary phases were classified and the quality of the chromatographic separation was estimated. The increase in the selectivity of smectic phases with the use of the cooling mode was rationalized thermodynamically.     

X-ray study of the nematic and smectic A phases of the cyano-substituted pyridines

We report an X-ray study of lamellar ordering in the nematic and smectic A phases of a homologous series of polar liquid crystals, the 2-(4-alkylphenyl)-5-cyanopyridines (nCP). Experiments were carried out using a diffractometer with a linear position sensitive detector. In the nematic and smectic A phases of the nCP and their mixtures with non-polar 4-n-butyl-4′-methoxyazoxybenzene two types of layering were found. One corresponds to the fluctuations of the smectic density wave with a monolayer wavevector q ₁, and the other is due to the partial bilayer fluctuations with the incommensurate wavevector q ₂ ≠ q ₁/2. The temperature dependences of the X-ray scattering intensity and the longitudinal correlation length for both types of layering in the nematic phase are presented. The critical behaviour in the vicinity of the smectic A-nematic phase transition occurs for a fluctuation mode, either q ₁ or q ₂, depending on the position on the liquid crystal phase diagram. The influence of the molecular structure of cyano-substituted pyridines on the formation of layered structures of different types is also discussed.     

Polybis(phosphinato)fluoroalanes

A new class of coordination polymers, polybis(phosphinato)fluoroalanes, [Al(F) (OPRR′O)_2n], where R,R′ are alkyl, phenyl, or benzyl, was prepared and studied. The properties of these polymers are influenced by the phosphinate (R) substituents; polymers having n-alkyl groups with more than five carbons are flexible and exhibit unusual hydrolytic stability. A polymer was obtained with a degree of polymerization of 104 by incorporating a 2:1 ratio of benzyl(n-heptyl) and di-n-octyl phosphinate groups. The properties of the flexible materials are consistent with linear rather than highly crosslinked or network systems. Feasible structures are proposed for the polymers.