Soft Crystal Phase Research Articles

Novel nanocomposites based on Tetrazine liquid crystals for energy storage application

Polymethyl methacrylate (PMMA) /Tetrazine liquid crystal (LCTZ12) nanocomposites with different CNTs loadings have been prepared. The prepared nanocomposites were characterized using polarizing light microscope (POM), differential scanning calorimetry (DSC), Fourier transform Infrared Spectroscopy (FTIR) and broadband dielectric spectroscopy (BDS) in the range 10-1-106 Hz respectively. The most commonly observed texture of soft crystal phases was that of a mosaic pattern, as revealed by the POM technique. PMMA alone does not change the polarization states and appeared as isotropic material, but once LCTZ12 is added, crystal growth could be clearly noticed in the needle pattern inside the polymer matrix to compose an amazing structure of soft crystal G texture. The increase of LCTZ12 to about 20 wt% in the PMMA matrix led to more heterogeneous aggregation of liquid crystalline molecules. This ratio addition is enhancing of network connections inside the PMMA. Moreover, the dispersion of carbon nanotubes mounted on catalysts is found to accumulate in segregations in PMMA/ LCTZ12 nanocomposites. However, the location of CNTs is concentrated at bottom of polymer network due to the large difference in densities of LCs, PMMA, and CNTs. DSC is in agreement with the POM result of LCTZ12, which has multi soft crystals or highly self-assembled ordered liquid crystal phases near to room temperature. The FTIR proved that blend PMMA/ LCTZ12 (80/20) has a dramatic increase in the 1387 cm−1 peak of C = C as a response of the rise in the concentration or number of aromatic rings. Additionally, the vibrational scissoring peak located at 1477 cm−1 of methylene CH2 groups is increased significantly and C–H stretching in aliphatic regions at 2850 cm−1 and 2990 cm−1 as well. However, there is no significant change observed after CNTs addition to the PMMA/ 20 wt% LCTZ12 matrix. Regarding dielectric results, it was found that, the polymer dispersed liquid crystals PDLC system composed of (PMMA/20 wt% LCTZ12) possesses the most promising dielectric properties, that is; high dielectric permittivity with low losses compared to the other ratios. The addition of CNTs results in more localization of charge carriers along with mobile ions, causing higher ionic conductivity. The conductivity ranges altered from 3.2 × 10-10 S/cm in pure PDLC system to become 1.7 × 10-3 S/cm for PDLC doped with 10 wt% CNTs nanocomposite. The electrical energy density measurements for 3,6-bis(5-(Dodecyloxy) pyridin-2-yl)-1,2,4,5-tetrazine (LCTZ12) liquid crystals with 6 cationic centers in polymeric matrices proved to be suitable for flexible and efficient electrolytes for energy storage devices.

Experimental and Computational Study of a Liquid Crystalline Dimesogen Exhibiting Nematic, Twist-Bend Nematic, Intercalated Smectic, and Soft Crystalline Mesophases.

Liquid crystalline dimers and dimesogens have attracted significant attention due to their tendency to exhibit twist-bend modulated nematic (NTB) phases. While the features that give rise to NTB phase formation are now somewhat understood, a comparable structure–property relationship governing the formation of layered (smectic) phases from the NTB phase is absent. In this present work, we find that by selecting mesogenic units with differing polarities and aspect ratios and selecting an appropriately bent central spacer we obtain a material that exhibits both NTB and intercalated smectic phases. The higher temperature smectic phase is assigned as SmCA based on its optical textures and X-ray scattering patterns. A detailed study of the lower temperature smectic ‘’X’’ phase by optical microscopy and SAXS/WAXS demonstrates this phase to be smectic, with an in-plane orthorhombic or monoclinic packing and long (>100 nm) out of plane correlation lengths. This phase, which has been observed in a handful of materials to date, is a soft-crystal phase with an anticlinic layer organisation. We suggest that mismatching the polarities, conjugation and aspect ratios of mesogenic units is a useful method for generating smectic forming dimesogens.

Liquid crystals from shape-persistent porphyrin stars with intrinsic free space

Shape-persistent porphyrin star mesogens form thin oriented films of columnar liquid crystal and soft crystal phases as a function of the conjugated arm scaffold.

Dielectric and electro-optic properties of two biphenylyl benzoate-based ferroelectric mesogens with tilted hexagonal phases

ABSTRACTTwo partially fluorinated ferroelectric liquid crystals (2F3R, 3F3R) with biphenylyl benzoate core have been investigated by frequency domain dielectric spectroscopy and electro-optic method. Both the compounds exhibit SmC* phase over a wide range of temperature along with tilted hexatic phase SmF* and soft crystal phases SmJ* (in 2F3R) and SmG* (in 3F3R) and one coexistence phase of (SmF*+SmC*). Both BOO phason and tilt phason relaxations are observed in SmF* phase and cooperative relaxation behaviour is also observed in crystal-like smectic phases. Goldstone mode relaxation is observed in SmC* phase and Maxwell Wagner mode is observed in all the phases. In 2F3R soft mode is detected in both SmC* and SmA* phases but not in 3F3R which melts directly to isotropic phase from SmC* phase. Compounds possess moderate values of spontaneous polarisation and exhibit quite sharp electrical response especially in 2F3R. Rotational viscosities, pitch and elastic constant are also measured. Effect of chain length and fluorination on various physical parameters has been discussed.

A Star-shaped Oligo(phenylenevinylene) Liquid Crystal Host with an Anthracene Guest-A Double Nanosegregating Supermesogen.

Hexasubstituted C3 -symmetric benzenes with three elongated shape-persistent oligo(phenylenevinylene) arms and three pyridyl hydrogen-bond acceptors have been synthesized. These mesogens assemble in a double-helical columnar liquid crystal (LC) structure, owing to the compensation of free spaces between conjugated arms by dimer formation. The void is filled also by up to three anthracene carboxylic acids as guests forming hydrogen bonded supermesogens assembling in columnar LC and soft-crystal phases. Thin film fluorescence and solid-state NMR spectroscopy imply a transition from a disordered columnar LC to an unexpected double nanosegregated morphology of a filled soft columnar crystal phase. An additional intracolumnar separation of anthracene and oligo(phenylenevinylene) chromophores occurs, separate to the general segregation of aliphatic and aromatic building blocks in LC structures. The new type of supermesogens will enable the rational design of host-guest double cables with a wide range of different conjugated building blocks.

Hexacatenars Exhibiting π-π Driven Supergelation, Aggregation Induced Blue Light Emission and Thermochromism

Two series of five ring polycatenars, which vary from each other with respect to the position of connection to the central benzene ring are reported. The overall shape of the molecule plays a major role than the number of flexible tails in the periphery in dictating the self-assembly (liquid crystallinity and gelation) and the photophysical behavior. Tetracatenars were crystalline and meta-substituted compounds exhibited reduced tendency to stabilize the mesophase. In the para-substituted series, all the hexacatenars exhibited columar hexagonal phase. p-Substituted hexacatenar with n-dodecyloxy tails exhibited thermochromism, with the highly emissive Colh phase and non-emissive soft crystal phase. Three p-substituted compounds exhibited supergelation exclusively promoted by π-π interactions. Besides the capability to form self-standing, moldable gel, one of the compounds exhibited technologically important aggregation-induced blue light emission. The columnar order and emissive nature in the aggregated state makes these molecules promising for the application in emissive displays.

3-(4-Bromophenyl)-5-(4-hydroxyphenyl)isoxazole: a versatile, new molecular building block for side-chain liquid crystal oligomers and polymers

The synthesis and liquid crystalline behaviour of new comb-shaped methacrylate oligomers, derived from a new key intermediate in the synthesis of heterocyclic liquid crystals, i.e., 3-(4-bromophenyl)-5-(4-hydroxyphenyl)isoxazole, are reported. These new thermotropic liquid crystals exhibit a smectic A mesophase (SmA) above a soft crystal phase (CrE). The new methacrylate oligomers were synthesized by free radical polymerization of the corresponding monomers. Additionally, one main-chain liquid crystal polymer (MCLCPs) was prepared using a Mizoroki–Heck polymerization. 3-(4-Bromophenyl)-5-(4-hydroxyphenyl)isoxazole (2) is a new key intermediate in the synthesis of polymer and non polymer ordered liquid crystal phase.

What makes a liquid crystal? The effect of free volume on soft matter

In this article, we probe the formation of liquid crystal and soft crystal phases as a consequence of minimising the free volume of the system either through design engineering of molecular shape or through deformation of molecular architecture. Following this concept, a number of realisations were made, for example, smectic A phases with variable layer spacing, smectic C phases without layer shrinkage, lattices of free space and fibres in NTB phases.

3,5-diarylisoxazoles: A New Entry to Soft Crystal Phase

This work describes the synthesis and characterization of a new liquid-crystalline compounds based on isoxazoles. Classical synthetic methodologies were employed in the preparation of this compounds, and the [3+2] 1,3-dipolar cycloaddition was the key step to prepare isoxazolines as precursors to isoxazoles. The structural and thermal characterization was performed using 1H and 13C NMR techniques, polarized-light optical microscopy and differential scanning calorimetry. Compounds 7a-e displayed the SmA mesophase. Soft crystal phase (CrE) was observed for compounds 7a and 7b containing chlorine and bromine atoms. For 7e containing a nitro group crystal phases below SmA mesophase were also observed.

Mesomorphic [2]Rotaxanes: Sheltering Ionic Cores with Interlocking Components

Two types of liquid crystalline [2]rotaxanes based on a conventional tetracatenar motif (a rod-shaped molecule with two side chains at each end) have been prepared. Dicationic compounds with ester stoppers and tetracationic materials with pyridinium stoppers are compared to each other and their dumbbell shaped analogs. Since the ionic core contributes about 70% to the overall length and molecular weight of the molecules, sheltering the ionic cores with an interlocked neutral macrocycle has considerable effect on the mesomorphism and thermal stability of the materials. The influence of the sheltering macrocycle, the numbers of charges on the core and the size and nature of the side chains (aliphatic vs siloxane) were probed. [2]Rotaxanes with linear side chains and minimum ratios of chain-to-core volumes of about 0.35 and 0.30 for tetra- and dicationic compounds, respectively, display smectic liquid crystal phases. Larger ratios increase the temperature range of the smectic A phases beyond the decomposition temperatures; a disadvantage for processing because no stable isotropic liquid phase is available. The change from tetra- to dicationic [2]rotaxanes increased not only the fluidity of their smectic A phases but also their thermal and chemical stability. Branched side chains (2-hexyldecyl) disfavor the formation of lamellar mesophases and, instead, induce higher ordered soft crystal phases. No liquid crystal phases but soft crystal phases are observed for the analogous di- and tetracationic compounds without an ion sheltering interlocked macrocycle (dumbbells).

Anthraquinone derivatives as electron-acceptors with liquid crystalline properties

Dialkoxy derivatives of anthraquinone (AQ), dicyano-anthraquinone (DCAQ) and tetracyanoanthraquinone (TCAQ) were synthesized and their associated electrochemical, optical and self-assembling properties were investigated as candidates for n-type materials. AQ shows UV absorption features, whereas both DCAQ and TCAQ exhibit bathochromic and hyperchromic electronic transitions into the visible region. The electron accepting strength of the three compounds was established by cyclic voltammetry as -1.52 V, -1.3 V and -0.9 V vs. ferrocene/ferricenium for AQ, DCAQ and TCAQ, respectively. All three quinones displayed quasireversible, two sequential one-electron transfer redox reactions. DFT calculations of DCAQ and TCAQ demonstrate structural changes upon reduction, which is supported by spectroelectrochemical experiments. Furthermore, the structural changes result in different absorption profiles and show potential as electrochromic materials. Finally, both AQ and DCAQ show liquid crystalline phases and importantly, DCAQ exhibits both a smectic liquid crystalline and a soft crystal phase between -6 °C and 85 °C, which offers promise as a self-assembling n-type material.

External-Stimuli Responsive Photophysics and Liquid Crystal Properties of Self-Assembled “Phosphole-Lipids”

A series of new amphiphilic phosphonium materials that combine the electronic features of phospholes with self-assembly features of lipids were synthesized. Variable concentration/temperature and 2D NMR studies suggested that the systems undergo intramolecular conformation changes between a "closed" and "open" form that are triggered by intermolecular interactions. The amphiphilic features of the phospholium species also induce liquid crystalline and soft crystal phase behavior in the solid state, which was studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable temperature powder X-ray diffraction (VT-PXRD). The studies revealed that both conjugated backbones and counteranions work together to organize the systems into different morphologies (liquid crystal/soft crystal). Dithieno[3,2-b:2',3'-d]phosphole-based compounds exhibit enhanced emission in the solid state and at low temperature in solution due to aggregation-induced enhanced emission (AIEE). Photoinduced electron transfer (PET) induced via the alkoxybenzyl group at the phosphonium center in the fused-ring systems can be effectively suppressed through intermolecular charge transfer (ICT) processes within the main scaffold of a nonfused system, which was confirmed by static and dynamic fluorescence spectroscopy. The dynamic features of these new materials also endow the systems with external-stimuli responsive photophysical properties that can be triggered by temperature and/or mechanical forces.

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.

Behavior of the layer compression elastic modulus near, above, and below a smectic C?hexatic I critical point in binary mixtures

We present the first study of the layer compression modulus B carried out near, above and below the Smectic C-Hexatic I critical point in racemic mixtures of methylbutyl phenyl octylbiphenyl-carboxylate (8SI) and the octyloxy biphenyl analog (8OSI), at frequencies ranging from 0.2 Hz to 2 x 10(3) Hz. The behavior of B as a function of temperature shows a progressive evolution from a first order transition in 8SI to a continuous supercritical behavior in 8OSI. The latter is characterized by an increase in B, which appears above the transition, and which is followed by a leveling off when the temperature is decreased towards the transition. It is proposed that this behavior stems from the relaxation of the hexatic domains which are frozen in the frequency range studied. For the supercritical and near-critical compounds, B exhibits a small dip near the transition temperature, which is visible in the low frequency range only, indicating that the dynamics associated with the critical point is very slow. We also report measurements in the Crystal-J phase of the pure compounds, and show that 8SI behaves mechanically as a hexatic phase and 8OSI as a soft crystal phase.