Novel chiral dimesogenic bidentate ligands and their Cu(II) and Pd(II) metal complexes

The synthesis and characterization of cholesterol-based dimesogenic bidentate ligands and their Cu(II) and Pd(II) metallomesogens are reported in detail. To understand structure-property relationships in these materials the terminal alkoxy chains and the central metal atom have been varied. Our studies reveal that chiral dimesogenic bidentate ligands with n -butyloxy chains exhibit smectic A (SmA), twist grain boundary and chiral nematic (N * ) mesophases while substitution with either n -decyloxy or 3,7-dimethyloctyloxy chains also show a ferroelectrically switchable chiral smectic C (SmC * ) mesophase. The metal complexes with n -butyloxy chains show only the SmA phase whereas higher chain length derivatives exhibit N * phase irrespective of the metal atom present. The ligands are thermally stable whereas their metal complexes, especially Pd(II) systems, seem to be heat sensitive. Spontaneous polarization, response time and tilt angle measurements have been carried out in the smectic C * phase of the two ligands.     

Cholesterol-based dimesogenic bidentate ligands and their Cu(II) and Pd(II) metallomesogens

The synthesis and evaluation of the liquid crystalline properties of non-conventional liquid crystals, consisting of two non-identical mesogenic segments interconnected via a paraffinic chain spacer, are of considerable current interest. In particular, chiral dimesogens possessing a cholesteryl ester unit as the chiral entity joined to other aromatic mesogens through a polymethylene spacer have shown unique and interesting thermal behaviour. In continuation of our investigations on this topic, here we present the synthesis and characterization of the first examples of cholesterol-based unsymmetrical dimesogenic bidentate ligands and their Cu(II) and Pd(II) metal-organic systems (metallomesogens). Our studies reveal that the dimesogenic bidentate ligands exhibit multiple mesophases, whereas their metal complexes stabilize only the mesophase.     

Cholesterol-based dimesogenic bidentate ligands and their Cu(II) and Pd(II) metallomesogens

The synthesis and evaluation of the liquid crystalline properties of non-conventional liquid crystals, consisting of two non-identical mesogenic segments interconnected via a paraffinic chain spacer, are of considerable current interest. In particular, chiral dimesogens possessing a cholesteryl ester unit as the chiral entity joined to other aromatic mesogens through a polymethylene spacer have shown unique and interesting thermal behaviour. In continuation of our investigations on this topic, here we present the synthesis and characterization of the first examples of cholesterol-based unsymmetrical dimesogenic bidentate ligands and their Cu(II) and Pd(II) metal-organic systems (metallomesogens). Our studies reveal that the dimesogenic bidentate ligands exhibit multiple mesophases, whereas their metal complexes stabilize only the mesophase.     

Achiral banana-shaped mesogenic bidentate ligands and their Cu(II) and Pd(II) complexes

The first achiral bent-core banana-shaped bidentate ligands and their Cu(II) and Pd(II) metal complexes have been synthesized and investigated for mesomorphic behaviour. The bidentate ligands exhibit only one enantiotropic mesophase. The ligand having C 6 -alkoxy chains shows a mesophase that has been assigned as a two-dimensional B 1 phase while the C 8 and C 10 homologues stabilize the fluid B 2 mesophase showing antiferroelectric switching characteristics. In constrast, their corresponding Cu(II) and Pd(II) metal complexes are non-mesomorphic.     

Achiral banana-shaped mesogenic bidentate ligands and their Cu(II) and Pd(II) complexes

The first achiral bent-core banana-shaped bidentate ligands and their Cu(II) and Pd(II) metal complexes have been synthesized and investigated for mesomorphic behaviour. The bidentate ligands exhibit only one enantiotropic mesophase. The ligand having C6 -alkoxy chains shows a mesophase that has been assigned as a two-dimensional B1 phase while the C8 and C10 homologues stabilize the fluid B2 mesophase showing antiferroelectric switching characteristics. In constrast, their corresponding Cu(II) and Pd(II) metal complexes are non-mesomorphic.     

Dimesogenic compounds consisting of cholesterol and azobenzene-based moieties: dependence of liquid crystal properties on spacer length and fluorination of the terminal chain

The liquid crystalline (LC) properties of two series of non-symmetric dimesogenic compounds consisting of cholesterol and azobenzene-based moieties interconnected by ω-oxyalkanoyl spacers of varying length are compared: one series (AOC-n) has an octyloxy chain attached to the azobenzene mesogen unit while the other (AOCF-n) has a perfluoroheptylmethyloxy chain. In general, compounds bearing the fluorinated alkoxy chain exhibited LC properties over a much broader temperature range than those with the alkoxy chain. In addition, the AOC-n series exhibited the chiral smectic C (SmC*), smectic A (SmA) and cholesteric (N*) phases depending on the length of the central spacer, whereas the AOCF-n series favoured the formation of only the SmA phase with the N* phase completely suppressed. Both series showed an odd-even dependence of the isotropization temperature on spacer length.     

The thermally sensitive characteristics of a (smectic LCP/ nematic LC/chiral dopant) ternary composite system

A transition between the transparent smectic A (SmA) phase and the light scattering chiral nematic (N*) phase was realized based on the thermally induced SmA N* phase transition for the homeotropically aligned \[liquid crystalline polymer (LCP)/liquid crystal (LC)/chiral dopant] ternary composite system. The LCP played an important role in increasing the intensity of the light scattering of the heat-induced N* phase. Meanwhile the effects of the composition of the ternary composite system on the thermo-optical characteristics were also investigated.     

Cholesterol-based dimeric liquid crystals: synthesis and mesomorphic behaviour

Chiral non-symmetric dimeric liquid crystals consisting of a cholesteryl ester moiety as chiral entity and a biphenyl aromatic core, interconnected through n-butyl (C₄) or n-pentyl (C₅) parity alkylene spacers, have been synthesized and investigated for their liquid crystalline properties. All the dimers exhibit enantiotropic mesophases. The first member of the dimers having the C₄ central spacer exhibit only the chiral nematic (N*) mesophase, while the higher homologues also show smectic A (SmA) and twist grain boundary (TGB) mesophases. The dimers of the other series containing the C₅ central spacer also have stable SmA, TGB and N* mesophases, except for the first which does not show the TGB phase. Both series of compounds show a weak odd-even effect with terminal alkyl chain substitution, while the spacer length has a marked influence on the phase transition temperatures.     

Influence of hydrogen bonding on phase abundance in ferroelectric liquid crystals

The synthesis and characterization of five hydrogen-bonded ferroelectric liquid crystal complexes (HBFLCs) prepared from mesogenic p-n-alkoxy benzoic acids and non-mesogenic propionic/butyric acids with different chiral centres are reported. Complementary intermolecular hydrogen bonding is confirmed through IR study. HBFLCs are found to exhibit chiral nematic (N*), smectic C* (SmC*) and smectic G* (monotropic) phases in their cooling profiles during polarizing thermal microscopy and differential scanning calorimetry. Phase coexistence regions are observed above the IN* transition. The chiral nematic to smectic C* transition is found to be of first order. The temperature variation of spontaneous polarization exhibited by these HBFLC complexes in their SmC* phase is presented. The effect of non-covalent interaction imparted by the soft hydrogen bonding in these LC complexes on enhanced or induced thermal stability of tilted LC phases is discussed.     

Electroclinic effect in the chiral smectic A and cholesteric phases at the proximity of a N*–SmA–SmC* multicritical point

We studied the electro-optic and dielectric properties of three pure ferroelectric liquid crystal materials (C10, C11 and C12) of the same series exhibiting cholesteric (N*), smectic A (SmA) and chiral smectic C (SmC*) phases. From electro-optic investigations, the tilt angle and spontaneous polarisation were determined as a function of temperature. In the dielectric measurements carried out without a dc bias field, we studied the soft-mode relaxation in the SmA phase. From experimental data and using the results of a Landau model, we evaluated the soft-mode rotational viscosity and the electroclinic coefficient in the SmA phase. A soft-mode like mechanism was also observed in the N* phase for compounds with shorter chains (C10 and C11). This relaxation process is not detected for the homologue with a longer chain (C12). The observation of this mechanism is related to smectic order fluctuations within N* phase whose amplitude is increased when approaching the SmC*–SmA–N* multicritical point.     

Thermal switching characteristics based on smectic-A↔chiral nematic phase transitions of (liquid crystals/chiral dopant) composites,with and without side chain-type liquid crystalline polymer

The light switching characteristics induced by a thermal smectic A (SmA) ? chiral nematic (N*) phase transition were studied for homeotropically aligned [smectic A liquid crystal (SmA-LC)/nematic liquid crystal (N-LC)/chiral dopant] and [side chain type smectic A liquid crystalline polymer (SmA-LCP)/N-LC/chiral dopant] composites. A drastic change from a transparent SmA phase to a light-scattering N* phase occurred in both composites upon heating. In the case of the heat-induced N* phase for the (SmA-LC/N-LC/chiral dopant) composite, the N* phase exhibited weak light scattering due to formation of a scroll texture. On the other hand, in the case of the heat-induced N* phase for the (SmA-LCP/N-LC/chiral dopant) composite, the N* phase showed strong light scattering due to formation of a focalconic texture. The existence of a SmA-LCP was responsible for a higher contrast ratio between the transparent SmA phase and the light scattering N* phase for the (SmA-LCP/ N-LC/chiral dopant) composite than for the (SA-LCN/N-LC/chiral dopant) composite.     

Liquid crystal dimers containing Cholesteryl and Triazole-containing mesogenic units

ABSTRACT

New liquid crystals categorised as cholesteryl dimers have been successfully synthesised through the reaction between cholesteryl 4-(prop-2-ynyloxy)benzoate moieties with n-azido(cholesteryloxy-carbonyl)alkane. All the dimers display enantiotropic mesophases. Whilst the odd-numbered dimers exhibit chiral nematic (N*), twisted grain boundary (TGB) and chiral smectic C (SmC*) phases, the even-numbered members from the same series show chiral smectic A and C. A detailed inspection on mesophase reveals that the chiral centres and the bent conformation of the odd-numbered members are essential for the induction of TGB phase. However, upon decreasing the temperature, the ratio of the transition temperatures (T_SmC*-SmA*/T_SmA*-I) is found to be 0.95, which indicate the second order transition according to the McMillan’s molecular theory. In addition, the X-ray diffraction study supports the presence of the smectic A phase on the even members rather than the N* by the appearance of the Bragg diffraction peaks at 190°C. A comparison study with the other analogues in which the cholesterol entity is substituted by azobenzene or biphenyl tails has been carried out to assess the relationship between the molecular structure and mesomorphic behaviour.     

Temperature dependent light transmission-light scattering switching of (homeotropic liquid crystalline polymer network/liquid crystals/chiral dopant) composite film

A (photo-polymerizable liquid crystal (LC) monomer/LCs/chiral dopant/photoinitiator) mixture with a smectic A (SmA)-chiral nematic (N*) phase transition was sandwiched between two ITO glass substrates which were not subjected to any surface orientation treatment. When an electric field-induced homeotropically oriented SmA phase of the mixture was irradiated with UV light, an oriented liquid crystalline polymer (LCP) network was formed upon photo-polymerization of the LC monomer. Then, a (homeotropically oriented LCP network/LCs/chiral dopant) composite with a SmA-N* phase transition was prepared. A focal-conic texture appeared in the heat-induced N* phase of the composite upon heating from the transparent state of the homeotropically oriented SmA phase; the focal-conic texture exhibited strong light scattering. Upon cooling the composite to the SmA phase, this phase was again homeotropically oriented due to the strong intermolecular interaction between the LC molecules and the homeotropically oriented LCP network. Thus, the transparent state of the SmA phase and the light scattering state of the N* phase occurred reversibly upon cooling and heating, accompanied by the thermal SmA-N* phase transition.     

Temperature dependent light transmission-light scattering switching of (homeotropic liquid crystalline polymer network/liquid crystals/chiral dopant) composite film

A (photo-polymerizable liquid crystal (LC) monomer/LCs/chiral dopant/photoinitiator) mixture with a smectic A (SmA)-chiral nematic (N*) phase transition was sandwiched between two ITO glass substrates which were not subjected to any surface orientation treatment. When an electric field-induced homeotropically oriented SmA phase of the mixture was irradiated with UV light, an oriented liquid crystalline polymer (LCP) network was formed upon photo-polymerization of the LC monomer. Then, a (homeotropically oriented LCP network/LCs/chiral dopant) composite with a SmA-N* phase transition was prepared. A focal-conic texture appeared in the heat-induced N* phase of the composite upon heating from the transparent state of the homeotropically oriented SmA phase; the focal-conic texture exhibited strong light scattering. Upon cooling the composite to the SmA phase, this phase was again homeotropically oriented due to the strong intermolecular interaction between the LC molecules and the homeotropically oriented LCP network. Thus, the transparent state of the SmA phase and the light scattering state of the N* phase occurred reversibly upon cooling and heating, accompanied by the thermal SmA-N* phase transition.     

Mesomorphic properties of troponoid esters and amides with cholest-5-ene-3β-carboxylic acid moiety

Troponoid esters and amides connected with cholest-5-ene-3β-carboxylic acid have been synthesized to characterize their mesomorphic properties and to compare them with those of the corresponding benzenoids. 5-Alkoxytroponyl esters and amides with a long alkoxy group exhibited a twist grain boundary A* phase, as well as chiral nematic and smectic A* (SmA*) phases. The corresponding benzenoid esters exhibit SmA* and blue phases and the benzenoid amides only a SmA* phase. The differences between the mesomorphic properties are discussed in terms of the structural features of the core.     

Rod-like phases formed by Ni(II) and VO(II) complexes of tetradentate enaminoketone ligands

Most of the nickel(II) complexes of tetradentate enaminoketone ligands obtained, although not strictly calamitic and with a rather low length to width ratio, form enantiotropic rod-like nematic and smectic A phases. Corresponding vanadyl(II) complexes exhibit only monotropic mesophases. The vanadyl complexes, due to their non-planar structure, are chiral with an asymmetry centre placed at the metal ion.     

Synthesis and liquid crystal properties of copper(II) and palladium(II) chelates with new ferrocene-containing enaminoketones

Heterometallic liquid crystals are of special interest because of the possibility to combine optical, magnetic and electric properties of different metal ions in one mesogenic molecule. In order to investigate new heteropolynuclear mesogenic systems, a series of β-aminovinylketone ligands derived from acetyl ferrocene have been synthesized. Subsequently Cu(II) and Pd(II) ions were incorporated into the enaminoketone chelate core. The obtained ligands and complexes were characterized by element analysis, ¹H NMR, IR and UV–Vis spectroscopies. According to thermal polarizing microscopy and DSC studies, the ligands and Cu(II) complexes exhibit disordered soft crystal phases upon cooling from the isotropic liquid state. The Pd(II) complexes showed monotropic smectic C mesomorphism. The metal centres in the synthesized heteropolynuclear mesogens are in close vicinity to each other, which is of considerable interest from the viewpoint of the potential electron-transfer interactions between a ferrocene core and the central ions.     

Coumarin based emissive rod shaped new schiff base mesogens and their zinc(II) complexes: synthesis,photophysical, mesomorphism,gelation and DFT studies

New homologous series of coumarin Schiff base derived from 6-aminocoumarin and their zinc(II) complexes have been synthesised. The spectroscopic characterisations, photophysical properties, phase transition temperature, characterisation of phase and gelation behaviour are reported. The ligand is non-mesogenic at lower 4-n-alkoxy chain length (n = 4) and mesogenic for longer chains (n > 4). For small chains (n = 5, 7, 8), ligand displays monotropic nematic or nematic-smectic A phase sequences, whereas longer homologues (n = 12, 14, 16 and 18) display only enantiotropic smectic A phase. The ligands and their Zn(II) complexes are fluorescent in nature. Interestingly, ligands exhibit gelation property only in polar solvents, whereas Zn(II) complexes discourage gelation. The effect of 4-n-alkoxy chain length on the gelation properties was also discussed. Density functional theory calculations show broad agreement with observed molecular conformation, dipole moment, molecular orbitals and polarisability of the coumarin Schiff base molecules and their Zn(II) complexes.     

The effect of the alkyl chain length on the mesomorphic properties of new lactic acid derivatives

New series of lactic acid derivatives with alkyl terminal chain have been synthesised and their mesomorphic properties studied. We have varied the length of chiral and non-chiral terminal alkyl chains and found that prolonging both chains has a strong effect on the SmA*–SmC* phase transition. Most of the new materials exhibit only paraelectric SmA* phase; for homologues with a longer non-chiral chain (m ≥ 10), the ferroelectric (SmC*) phase appears below the SmA* on cooling and persists down to a room temperature. The role of the chiral terminal chain in the molecule is quite opposite – only its short length supports the existence of ferroelectric phase. Additionally, a hexatic phase appeared below the SmA*–SmC* phase sequence for several homologues at low temperatures. All materials have been studied using standard experimental techniques (differential scanning calorimetry (DSC), texture observations, polarisation and tilt angle measurements, etc.). Liquid crystalline properties of new materials have been compared with the previously prepared and studied lactic acid derivatives.     

Spacer length dependence of TGBC* and SmA phases in cholesteryl and dihydrocholesteryl-containing trimer liquid crystals

Two series of trimer liquid crystals were investigated that contain a biphenylyl central group and two cholesteryl or dihydrocholesteryl terminal mesogenic groups. Only compounds with even spacers were investigated. The dihydrocholesteryl-containing trimers show a triply intercalated smectic A (SmA) phase when the spacer lengths are greater than 8, whereas the cholesteryl-containing trimers exhibit this triply intercalated SmA phase when the spacer lengths are more than 6. With shorter spacers, a twist grain boundary C* (TGBC*) phase was found. This is revealed by the formation of a typical dotted square grid pattern upon cooling from the chiral nematic (N*) phase in the planar texture. The dots are spaced by a distance of about 1.5-1.8 µm. Upon cooling from the N* phase in the focal conic texture a striped pattern is observed with the same spacing. X-ray diffraction revealed a repeat distance for the TGBC* phase that corresponds with a monolayer ordering. The results show that the weaker interaction between the dihydrocholesteryl groups compared with cholesteryl groups or longer spacers destabilize the monolayer TGBC* phase.