Light induced shifts of ferroelectric mesophase transitions

Several series of recently synthesized chiral azobenzene liquid crystals exhibit transitions driven by both illumination and temperature: some compounds can be 'melted' from the SmC* phase to the isotropic phase by increasing illumination only; according to the phase sequences, SmA, TGBA, N*, and blue phases are also involved in such behaviour. The observed phenomena are reversible and transition temperatures are reproducible in identical light conditions. Some specific transitions have been studied. Their temperatures can be lowered to 10 degrees below the dark transition values by increasing the illumination of samples. Under illumination, those transitions exhibit first order behaviour.     

Fourier transform infrared investigation of the effects of irradiation on the 19 and 30°C phase transitions in polytetrafluoroethylene

Fourier transform infrared spectroscopy has been used in conjunction with differential scanning calorimetric measurements to investigate the nature of molecular degradation and its effect on the phase transition temperatures in irradiated polytetrafluoroethylene (PTFE). Both the 19 and 30°C transitions are observed to exhibit similar shifts to low temperatures upon irradiation. Infrared absorbance subtraction data from irradiated PTFE indicate a continual decrease in sample crystallinity accompanied by an increase in the number of free and bonded ? COOH groups with increasing dose consistent with molecular degradation by chain scission. By comparing infrared band intensities on a number of irradiated PTFE samples with those from short chain perfluoro n-alkanes, it was determined that the overall reduction in chain length caused by irradiation was primarily responsible for the observed reduction in both phase transition temperatures.     

Density studies in terephthalylidene-bis-p-n-alkylanilines

Abstract

The temperature dependence of density in terephthalylidene-bis-p-n-alkylanilines (TBAA5 and 6) is studied to investigate the phase transitions, associated volume jumps, order of the transitions, estimated pressure dependence of transition temperatures, and pretransitional effects. The compounds exhibit nematic, smectic A, smectic C, smectic F, smectic G and smectic H phases with higher clearing temperatures. The smectic A to smectic C transition, which is a fluctuation induced first order transition in TBAA5, is found to be a second order transition in TBAA5 and 6. The results are discussed in the light of other experimental reports. The estimated pressure dependence of transition temperatures along with the reported experimental P[sbnd]T data are discussed. The N[sbnd]S_A transition is first order in TBAA5 and 6. The studies across other transitions are also discussed.     

Crystal Structures and Phase Sequences of Metallocenium Salts with Fluorinated Anions: Effects of Molecular Size and Symmetry on Phase Transitions to Ionic Plastic Crystals

Sandwich compounds often exhibit various phase transitions, including those to plastic phases. To elucidate the general features of the phase transitions in metallocenium salts, the thermal properties and crystal structures of [Fe(C₅Me₅)₂]X ([ 1 ]X), [Co(C₅Me₅)₂]X ([ 2 ]X), and [Fe(C₅Me₄H)₂]X ([ 3 ]X) have been investigated, where the counter anions (X) are Tf₂N (=(CF₃SO₂)₂N^?), OTf (=CF₃SO₃^?), PF₆, and BF₄. The Tf₂N salts commonly undergo phase transitions from an ordered phase at low temperatures to an anion‐disordered phase, followed by a plastic phase and finally melt at high temperatures. All these salts exhibit a phase transition to a plastic phase, and the transition temperature generally decreases with decreasing cation size and increasing anion size. The crystal structures of these salts comprise an alternating arrangement of cations and anions. About half of these salts exhibit phase transitions at low temperatures, which are mostly correlated with the order–disorder of the anion.     

Phase behaviour of poly-(λ-benzyl-L-glutamate) in benzyl alcohol

Polarized optical microscopy has been used to investigate phase transitions in the poly-(λ-benzyl-L-glutamate) benzyl alcohol system and these have been compared with the predictions of Flory. All of the samples studied form gels at room temperature. The behaviour of the lowest concentration studied, 5 per cent by volume, shows transitions in the optical microscope compatible with the Flory phase diagram, becoming isotropic at elevated temperatures. Gels of higher concentrations exhibit bulk phase separation into an isotropic liquid phase and an anisotropic phase at room temperature, also in accord with the Flory predictions; the texture of the anisotropic phase varies with concentration. At higher temperatures these concentrations exhibit two coexistent anisotropic phases.     

Density studies in terephthalylidene-bis-p-n-alkylanilines

The temperature dependence of density in terephthalylidene-bis-p-n-alkylanilines (TBAA5 and 6) is studied to investigate the phase transitions, associated volume jumps, order of the transitions, estimated pressure dependence of transition temperatures, and pretransitional effects. The compounds exhibit nematic, smectic A, smectic C, smectic F, smectic G and smectic H phases with higher clearing temperatures. The smectic A to smectic C transition, which is a fluctuation induced first order transition in TBAA5, is found to be a second order transition in TBAA5 and 6. The results are discussed in the light of other experimental reports. The estimated pressure dependence of transition temperatures along with the reported experimental P-T data are discussed. The N-S_A transition is first order in TBAA5 and 6. The studies across other transitions are also discussed.     

The effect of some phenyltin compounds on the thermotropic phase behaviour and the structure of model membranes

The effects of diphenyltin dichloride (DPhT), triphenyltin chloride (TPhT) and tetraphenyltin (TTPhT) on the thermotropic phase behaviour of phosphatidylcholine bilayers were studied. All the phenyltin compounds investigated affected phase transitions differently. TTPhT broadened the main phase transition but it left the transition temperatures and enthalpy unchanged. TPhT reduced the transition temperatures and the enthalpies while DPhT showed a dual effect on the pretransition and the main transition. At low concentrations DPhT reduced the temperatures of the transitions slightly and at higher concentrations it increased them. Based on differential scanning calorimetry (DSC) and also ¹H NMR and ³¹P NMR measurements, it is suggested that DPhT induces interdigitated gel phase formation and TPhT induces hexagonal phase formation. TTPhT seems to affect the structure only a little. The toxic activity of DPhT and TPhT seems to be connected with their ability to induce changes in the membrane structure. Copyright © 2000 John Wiley & Sons, Ltd.     

Trimeric liquid crystals containing lateral alkyl chains

The first twelve members of the n-alkyl 2,5-bis-(4'-cyanobiphenyloxybutyloxy)-benozates have been prepared. The compounds are nematogenic; in addition the first three members exhibit a smectic A phase. The nematic-isotropic transition temperatures decrease with little or no alternation on increasing the number of methylene groups in the lateral chain; this is analogous to the behaviour found in monomeric and polymeric mesogens possessing lateral alkyl chains.     

Overlap of colloid chemistry and photochemistry in surfactant systems

Interactions of organic photochemistry and colloid chemistry in surfactant systems can be divided in two distinct sections: (i) influences of the colloids on photochemical reactions and (ii) influences of photochemical reactions on macroscopic properties of colloidal surfactant systems. As to (i), the (generally poor) selectivity of photochemical reactions can be improved by performing the reactions in systems containing surfactant aggregates. Regioselectivity, stereoselectivity and multiplicity selectivity can be directed. As to (ii), in lyotropic liquid crystalline systems the solubilization of certain aromatic compounds specifically changes phase transition temperatures. Upon photochemically transforming such solubilizates in situ isothermal phase transitions can be brought about, provided that photoeducts and photoproducts induce distinct transition temperatures. Similarly in dilute surfactant systems solubilizates specifically affect size and shape of micellar aggregates, so that changes in flow behaviour take place, which can be switched via photochemical transformation of solubilizates. Possible exploitations of the effects are discussed and compared with the application of similar effects in related non-surfactant systems, with emphasis on photochemical information storage.     

Trimeric liquid crystals containing lateral alkyl chains

Abstract

The first twelve members of the n-alkyl 2,5-bis-(4′-cyanobiphenyloxybutyloxy)-benozates have been prepared. The compounds are nematogenic; in addition the first three members exhibit a smectic A phase. The nematic-isotropic transition temperatures decrease with little or no alternation on increasing the number of methylene groups in the lateral chain; this is analogous to the behaviour found in monomeric and polymeric mesogens possessing lateral alkyl chains.     

Novel photo-crosslinkable liquid crystalline polymers containing vanillylidene cycloalkanones and azobenzene units

Two series of novel liquid crystalline photo-crosslinkable bis(vanillylidene-azobenzene) cycloalkanone containing polymers, namely poly(vanillylidene alkyloxy-4,4'-azobenzenedicarboxylic ester)s, have been synthesised from bis[m-hydroxyalkyloxy(vanillylidene)cycloalkanone] (m = 6, 8, 10) with azobenzene dicarbonylchloride by solution polycondensation method at ambient temperature. Polymers with varying spacer lengths have been synthesised and characterised by spectroscopic techniques. These variations have been correlated with the thermal properties and transition temperatures. Thermal transitions were analysed by differential scanning calorimetry (DSC) and the mesophases were identified by hot stage optical polarised microscopy (HOPM). All of the polymers were found to exhibit liquid crystalline properties. Transition temperatures were observed to decrease with increasing spacer length. The thermogravimetric analysis reveals that all of the polymers were stable up to 280°C undergo two-stage decomposition. Using the UV-visible photolysis studies we investigated the simultaneous behaviour of reactivity rates of crosslinking in the vanillylidene unit and isomerisation caused by the azobenzene unit in the photo-crosslinkable main chain liquid crystalline polymers. The photolysis of liquid crystalline bis(vanillylidene)cycloalkanone-based polymers reveals that there are two kinds of photoreactions in these systems: the EZ photoisomerisation of azobenzene unit and 2p+2p addition by vanillylidene units. The EZ photoisomerisation in the liquid crystal phase disrupts the parallel stacking of the mesogens, resulting in the transition from the liquid crystal phase to isotropic phase. The photoreaction involving 2p+2p addition of the bis(vanillylidene)cycloalkanone units in the polymers results in the conjoining of the chains. The cyclopentanone polymers exhibited a faster rate of photolysis than the cyclohexanone polymers.     

Influence of chirality on phase transitions in ferroelectric liquid crystals

The transition temperatures between various smectic liquid crystal phases are determined as a function of the enantiomeric excess for three different chiralracemic systems (i.e. binary mixtures consisting of a chiral enantiomer and its racemate). It is shown that transitions involving a ferroelectric phase occur in the chiral compounds at higher temperatures compared to their racemates, the temperature shift being proportional to the square of the enantiometric excess. In contrast, for transitions between two non-ferroelectric phases no difference between the chiral and the racemic compounds is found. Various reasons for the experimental behaviour are discussed. A chirality dependence of the transition temperature is also observed for the smectic A-isotropic transition.     

Novel photo‐crosslinkable liquid crystalline polymers containing vanillylidene cycloalkanones and azobenzene units

Two series of novel liquid crystalline photo‐crosslinkable bis(vanillylidene‐azobenzene) cycloalkanone containing polymers, namely poly(vanillylidene alkyloxy‐4,4′‐azobenzenedicarboxylic ester)s, have been synthesised from bis[m‐hydroxyalkyloxy(vanillylidene)cycloalkanone] (m = 6, 8, 10) with azobenzene dicarbonylchloride by solution polycondensation method at ambient temperature. Polymers with varying spacer lengths have been synthesised and characterised by spectroscopic techniques. These variations have been correlated with the thermal properties and transition temperatures. Thermal transitions were analysed by differential scanning calorimetry (DSC) and the mesophases were identified by hot stage optical polarised microscopy (HOPM). All of the polymers were found to exhibit liquid crystalline properties. Transition temperatures were observed to decrease with increasing spacer length. The thermogravimetric analysis reveals that all of the polymers were stable up to 280°C undergo two‐stage decomposition. Using the UV–visible photolysis studies we investigated the simultaneous behaviour of reactivity rates of crosslinking in the vanillylidene unit and isomerisation caused by the azobenzene unit in the photo‐crosslinkable main chain liquid crystalline polymers. The photolysis of liquid crystalline bis(vanillylidene)cycloalkanone‐based polymers reveals that there are two kinds of photoreactions in these systems: the EZ photoisomerisation of azobenzene unit and 2p+2p addition by vanillylidene units. The EZ photoisomerisation in the liquid crystal phase disrupts the parallel stacking of the mesogens, resulting in the transition from the liquid crystal phase to isotropic phase. The photoreaction involving 2p+2p addition of the bis(vanillylidene)cycloalkanone units in the polymers results in the conjoining of the chains. The cyclopentanone polymers exhibited a faster rate of photolysis than the cyclohexanone polymers.     

Synthesis, characterization and phase transitions of the inorganic-organic layered perovskite-type hybrids [(C(n)H(2n+1)NH3)2PbI4], n = 7, 8, 9 and 10

Four inorganic-organic hybrid materials that consist of 2-D layers of corner-sharing lead(II) iodide octahedra separated by alkylammonium chains have been crystallized and characterized via single-crystal XRD (SCXRD). The four hybrids, represented by the general formula [(C(n)H(2n+1)NH(3))(2)PbI(4)] and abbreviated C(n)PbI, exhibit multiple reversible phase transitions for a narrow temperature range. The transition temperatures were determined with differential scanning calorimetry experiments. The number of transitions and the transition temperatures are dependant on the chain length; for n = 7 and 10, there are three transitions, and for n = 8 and 9, there are two transitions. Regardless of the number of transitions, all four compounds have identical lowest temperature phases, which have inorganic layers that are eclipsed, non-planar conformations of the alkyl ammonium chains and yellow-coloured crystals. The next highest temperature phase for three of the compounds (C(10)PbI goes through an intermediate phase first), has staggered inorganic layers, all-trans planar conformations of the chains and orange coloured crystals. The highest temperature phase for n = 8 and 10 has red-coloured crystals and shows a disordering of the alkylammonium chains over two positions and staggered inorganic layers. The high temperature phase of C(7)PbI retains its orange colour and has only increased thermal motion of its alkylammonium chain. The structure of the high temperature phase of C(9)PbI was not determined. The SCXRD structures of the various phases give clues to the structural changes that the compounds undergo at the phase transitions, which will now enable future studies of their optical and electronic properties to be better understood.     

Investigations on the melting behaviour of triglyceride nanoparticles

Suspensions of triglyceride nanoparticles have been proposed as carrier systems for intravenous administration of poorly water soluble drugs. Such nanosuspensions can easily be produced by homogenization of the melted triglyceride in an aqueous phase. Using special emulsifier blends it is possible to obtain suspensions with an average size of the recrystallized particles below 100 nm (photon correlation spectroscopy z-average). As can be observed by transmission electron microscopy the particles are very thin platelets with thicknesses in the range of only a few molecular layers. Nanoparticles of saturated monoacid triglycerides (smaller than 200 nm) exhibit uncommon melting behaviour, which is expressed in their differential scanning calorimetry curve by multiple endothermal peaks over a temperature range of about 10 °C. This effect was attributed earlier to the particle thickness distribution in the suspension rather than to polymorphic transitions since all the material exists in the stable β modification. Here we present experimental investigations on the correlation between the melting behaviour of trilaurin nanosuspensions and the particle thickness distribution determined by analysis of difference X-ray diffraction patterns recorded at progressively higher temperatures in the melting range of the particles. Because of the weak X-ray scattering of the systems investigated synchrotron radiation was used besides conventional sources. The Fourier analysis of the difference diffraction patterns is described in detail and the advantages and difficulties in using this method are discussed. It was observed that the melting temperatures of the nanoparticles increase with increasing particle thicknesses. Simultaneously a decrease in the interplanar (001) spacing with increasing particle thickness was found. Received: 27 July 1999 Accepted: 5 October 2000     

Synthesis and characterization of side‐chain liquid‐crystalline poly(ethyleneimine)s with cyanobiphenyl groups

A series of polyethyleneimine‐based side‐chain liquid‐crystalline polymers substituted with different ratios of cyanobiphenyl as pendent mesogenic groups has been synthesized in which the spacer length varies between two and six methylene units. The structures of the synthesized polymers are confirmed by infrared and ¹H nuclear magnetic resonance spectroscopy. The thermal properties of these polymers have been investigated using differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. The results indicate that the thermal behaviour of the polymers is strongly dependent on the degree of substitution. Polymers containing more than 69% of mesogenic groups exhibit nematic‐type thermotropic liquid‐crystalline behaviour with schlieren textures. Below this limit, the polymers are amorphous. Polymers with a higher degree of substitution present the crystalline states. The phase transition temperatures increase and the mesomorphic temperature ranges widen with increasing degree of substitution. The clearing temperatures decrease as the spacer length increases. An odd–even effect in the clearing temperatures is observed and the odd members display the higher values.     

Solution behaviour in alcohols and phase transitions of cadmium(II), mercury(II) and lead(II) carboxylates

Data were obtained for the solution behaviour of cadmium(II) and mercury(II) carboxylates in alcohols. A brief survey of the arguments about the existence of micelles and the current models of surfactant aggregation in non-aqueous media is presented. The plots of solubility against the carboxylate or alcohol chain length are linear for both cadmium and mercury soaps with the solubility having values higher in secondary than primary alcohols. The solution behaviour of metal 9, 10-dihydroxyoctadecanoates shows the effect on solubility, of substitution of dihydroxyl groups at the middle of the carbon chain. Recrystallisation temperatures of the dihydroxyoctadecanoates suggest the loss of stereochemical configuration in solution and indicate similarity in the mode of aggregation. The solution temperatures of cadmium soaps are very close to the temperatures of their phase transitions while those of mercury and lead soaps are lower than their fusion or phase transition temperatures. This behaviour is interpreted to be due to differences in the energy required for the disruption of the crystal structure which dominates the solubility mechanism.     

Synthesis of novel nematic liquid crystals containing 3,3'-dimethyl-2,2'-bipyridyl

Liquid-crystalline 3,3'-dimethyl-2,2'-bipyridyl derivatives with long 4-(alkoxyphenyl)ethynyl (-C=C-C₆H₄-OR) groups in the 5,5'-positions were synthesized by palladium-catalysed crosscoupling reactions. The compounds exhibit exclusively nematic behaviour; for example, the hexyl derivative showed a nematic phase over the temperature range 145.2-205.0°C. On increasing the length of the terminal chain, the transition temperatures were lowered; for example, the hexadecyl derivative was nematic in the range 117.0-126.8°C.     

Mesomorphism of lanthanide-containing Schiff's base complexes with chloride counterions

Liquid crystalline complexes [Ln(LH)3Cl3] have been synthesized, where Ln is a trivalent lanthanide ion (Pr-Lu, except Pm) and where LH is the Schiff's base ligand N-octadecyl4-tetradecyloxysalicylaldimine. Although the ligand does not exhibit mesomorphism, the complexes do (SmA phase). The mesophase behaviour of these compounds has been investigated by polarizing optical microscopy, differential scanning calorimetry and high temperature X-ray diffraction. The lanthanide complexes have much higher melting and clearing points than comparable complexes with nitrate or dodecyl sulphate counterions. In addition, the transition temperatures are virtually independent of the type of lanthanide ion. This behaviour is opposite to that observed for similar complexes with nitrate counterions [Ln(LH)3(NO3)3]. The differences in temperature dependence can be related to structural differences. Whereas in the nitrate complexes the Schiff's base ligand binds in a zwitterionic form, two-dimensional 1H NMR correlation spectroscopy (COSY) of [Lu(LH)3Cl3] gives an indication that in the chloride complexes, besides coordination via the oxygen of molecules in the zwitterionic form, some of the Schiff's base ligands bind in a bidentate fashion (via the phenolic oxygen and the imine nitrogen).     

Thermal phase transitions of solid chiral N,N′-carbonyl-bis-(l-amino acids) and their methyl and benzyl esters

Compounds derived from different N,N′-carbonyl-bis-(l-amino acids) and their methyl and benzyl esters were synthesized and characterized by elemental analysis, infrared and nuclear magnetic resonance. The amino acids used were valine, leucine, phenylglycine and phenylalanine. All compounds revealed complex thermal behaviour as proved by differential scanning calorimetry, X-ray powder diffractometry and optical birefringence observation by polarizing microscope. Above isotropization temperature N,N′-carbonyl-bis-(l-amino acids) decomposed. The number and kinds of thermal phase transitions of investigated esters vary from a simple phase transition and melting to a complex polymorphism, and strongly depends on molecular structure. One to four phase transitions have been observed upon heating. Phase transition temperatures showed considerable variation with choice of the supstituent on symmetric carbons and therminal carboxylic groups. The results are discussed in terms of the architecture of investigated molecules that hinder mesomorphism.