Smectic Liquid Crystalline Phase Research Articles

Supramolecular Arrangement and Conformational and Dynamic Properties of Chiral Smectic Liquid Crystals Obtained through Nuclear Magnetic Resonance: A Brief Review

Ferroelectric and antiferroelectric smectic liquid crystalline (LC) phases are still at the center of investigations and interests for both their fundamental properties and variety of technological applications. This review aims to report the main contributions based on different nuclear magnetic resonance (NMR) techniques to the study of chiral liquid crystalline calamitic mesogens forming smectic phases, such as the SmA, the SmC* (ferroelectric), and the SmC*A (antiferroelectric) phases. 2H NMR and 13C NMR techniques and their combination were of help in clarifying the local orientational properties (i.e., the molecular and fragments’ main orientational order parameters) at the transition between the SmA and the SmC* phases, and in the particular case of de Vries liquid crystals, NMR studies gave important clues regarding the actual models describing the molecular arrangement in these two phases formed by de Vries LCs. Moreover, this review describes how the combination of 2H NMR relaxation times’ analysis, 1H NMR relaxometry, and 1H NMR diffusometry was successfully applied to the study of chiral smectogens forming the SmC* and SmC*A phases, with the determination of relevant parameters describing both rotational molecular and internal motions, collective dynamics, and translational self-diffusion motions. Several cases will be reported concerning NMR investigations of chiral ferroelectric and antiferroelectric phases, underlining the great potential of combined NMR approaches to the study of supramolecular, conformational, and dynamic properties of liquid crystals.

Thermoresponsive supramolecular nanocontainers from ionic complexes of amphiphilic wedge-shaped mesogens and polybases

Multi-responsive polymeric nanocontainers attract significant attention for their potential applications in biotechnology, drug delivery, catalysis, and other fields. By incorporating a liquid-crystalline (LC) mesogenic ligand with an alkyl tail length ranging from 8–12 carbons, ionically linked to the polymer backbone, we generate vesicles with walls significantly thinner than those of conventional polymersomes, approaching the thickness of a lipid bilayer. These LC vesicles, ranging in size from 50–120 nm, are designed to be mechanically robust due to the alignment of the hydrophilic polymer backbone within the plane of the vesicle wall. Additionally, incorporating a temperature-sensitive block into the polymer structure imparts thermoresponsiveness to the nanocontainers, enhancing their functionality and adaptability for various applications. Ionic complexes of hydrophilic polybases, specifically poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and PDMAEMA-b-PNIPAM (poly(N-isopropylacrylamide)) block copolymers, with amphiphilic wedge-shaped mesogens bearing a sulfonic acid group at the focal point were synthesized. The designed nanocontainers, in the form of either vesicles or nanotubes, exhibit a well-defined wall thickness of 5 nm, dictated by the organization of a smectic LC phase. The constructed coarse-grained models elucidate the mechanism of self-assembly, demonstrating that the balance between the hydrophilicity of the main polymer chain and the hydrophobicity of the wedge-shaped pendant groups determines both the internal and external structure of the vesicles.

Magnetorheological liquid-crystalline polymers with magnetic tetrachloroferrate ions based on polyvinyl chloride

ABSTRACT Novel magnetic ionic polymers based on polyvinyl chloride ([PVCs][FeCl4]) with liquid-crystalline (LC) ordering were synthetised and characterised. The [PVCs][FeCl4] containing magnetic tetrachloroferrate ions were prepared with PVC, pyridyl LC monomers and FeCl3. Various devices and instruments were used to characterise the chemical structure, thermal behaviour, magnetic properties, and LC properties. The synthetised [PVCs][FeCl4] showed smectic LC phase and presented excellent thermal stability. Several magnetorheological (MR) fluids were prepared using [PVCs][FeCl4] as particles and silicone oil as carrier fluid. MR Effects and settlement stability were investigated. Under the condition of external magnetic field, the MR fluids showed Bingham flow characteristics, and the MR effect was enhanced with increasing FeCl4 − content in the systems. Under the condition of magnetic field intensity of 80 kA/m and shear rate of 2.5 s−1, the magnetorheological efficiency of [PVCs][FeCl4] based MR fluids with particle concentration of 20% can reach up to 14.7. The excellent MR effect of [PVCs][FeCl4] was due to the strong coupling between the magnetic moment of the FeCl4 − anion and the orientation of cationic LC primitive under the action of an applied magnetic field. Furthermore, the good settling stability of the MR fluids was due to the introduction of organic mesogens, PVC main-chains and the ionic components for the [PVCs][FeCl4] particles.

Synthesis of Calamitic Fluorinated Mesogens with Complex Crystallization Behavior.

This work presents the synthesis and self-organization of the calamitic fluorinated mesogen, 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-4-iodobutoxy)ethanesulfonic acid, a potential model for perfluorosulfonic acid membranes (PFSA). The compound is derived in three steps from 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-iodoethoxy)ethanesulfonyl fluoride, achieving a 78% overall yield. The resulting compound exhibits intricate thermal behavior. At 150 °C, a crystal-to-crystal transition is observed due to the partial disordering of calamitic molecules, which is followed by isotropization at 218 °C. Upon cooling, sample ordering occurs through the formation of large smectic liquid crystalline phase domains. This thermotropic state transforms into a layered crystal phase at lower temperatures, characterized by alternating hydrophilic and hydrophobic layers. Using X-ray diffraction, crystalline unit cell models at both room temperature and 170 °C were proposed. Computer simulations of the molecule across varying temperatures support the idea that thermal transitions correlate with a loss of molecular orientation. Importantly, the study underscores the pivotal role of precursor self-organization in aligning channels during membrane fabrication, ensuring controlled and oriented positioning.

Synthesis and Characterization of Side-Chain Liquid-Crystalline Block Copolymers Containing Cyano-Terminated Phenyl Benzoate Moieties

Block copolymers, known for their capacity to undergo microphase separation, spontaneously yield various periodic nanostructures. These precisely controlled nanostructures have attracted considerable interest due to their potential applications in microfabrication templates, conducting films, filter membranes, and other areas. However, it is crucial to acknowledge that microphase-separated structures typically exhibit random alignment, making alignment control a pivotal factor in functional material development. To address this challenge, researchers have explored the use of block copolymers containing liquid-crystalline (LC) polymers, which offer a promising technique for alignment control. The molecular structure and LC behavior of these polymers significantly impact the morphology and alignment of microphase-separated structures. In this study, we synthesized LC diblock copolymers with cyano-terminated phenyl benzoate moieties and evaluated the microphase-separated structures and molecular alignment behaviors. The LC diblock copolymers with a narrow molecular weight distribution were synthesized by atom transfer radical polymerization. Small angle X-ray scattering measurements revealed that the block copolymers exhibit smectic LC phases and form cylinder structures with a lattice period of about 18 nm by microphase separation. The examination of block copolymer films using polarized optical microscopy and polarized UV-visible absorption spectroscopy corroborated that the LC moieties were uniaxially aligned along the alignment treatment direction.

Supramolecular Liquid Crystal Carbon Dots for Solvent-free Direct Ink Writing.

Recent years have witnessed the major advances of nanolights with extensive exploration of nano-luminescent materials like carbon dots (CDs). However, solvent-free processing of these materials remains a formidable challenge, impeding endeavors to develop advanced manufacturing techniques. Herein, in response to this challenge, liquid crystallization is demonstrated as a versatile and robust approach by deliberately anchoring flexible alkyl chains on the CDs surface. Alkyl chain grafting on the CDs surface is observed to substantially depress the common aggregation-caused quenching effect, and results in a shift of self-assembly structure from the crystalline phase to smectic liquid crystalline phase. The liquid crystalline phase transition temperature is ready to adjust by varying the alkyl chain length, endowing low temperature (< 50°C) melt-processing capabilities. Consequently, the first case of direct ink writing (DIW) with liquid crystal (LC) carbon dots is demonstrated, giving rise to highly emissive objects with blue, green and red color fluorescence, respectively. Another unexpected finding is that the DIW with LC inks dramatically outperforms the DIW with isotropic inks, further highlighting the significance of LC processing. The reported approach herein not only exhibits a fundamental advance by imparting LC functions to CDs, but also promises technological utility in DIW-based advanced manufacturing. This article is protected by copyright. All rights reserved.

Pd(II)-complexes of telluro-substituted Schiff base ligands: Effect of the pendant alkyl group on Suzuki and Heck coupling through in situ generated palladium nanoparticles

Two telluro-substituted Schiff bases L1/L2 having different pendant carbon chains (−Me in L1 and − C10H21 in L2) and their corresponding square planar Pd(II)-complexes (1/2) have been synthesized and their structural characterization has been carried out using multinuclear NMR and elemental analysis. The ligand L2 showed a Smectic liquid crystalline phase and melts at 81 °C into isotropic liquid whereas L1 and complexes (1/2) did not show any liquid crystalline property. The square planar Pd(II)-complexes (1/2) have been formed through the coordination of ligands (L1/L2) respectively in mono-anionic tridentate mode (Te,N,O−) and the fourth coordination sphere at the palladium center is occupied with chloride ion. Both complexes 1/2 (1 to 2 mol%) have beenexamined as a catalyst for Suzuki and Heck coupling reactions and their activity depends significantly on the length pendant alkyl chain. The results obtained from Hg-/PPh3-poisoning and three phase test on Suzuki-Miyaura coupling indicate the participation of both homogeneous as well as heterogeneous palladium species protected with the ligand or its fragment.

Fully Room Temperature Reprogrammable, Recyclable, and Photomobile Soft Actuators from Physically Cross-Linked Main-Chain Azobenzene Liquid Crystalline Polymers.

Fully room temperature three-dimensional (3D) shape-reprogrammable, recyclable, and photomobile azobenzene (azo) polymer actuators hold much promise in many photoactuating applications, but their development is challenging. Herein, we report on the efficient synthesis of a series of main-chain azo liquid crystalline polymers (LCPs) with such performances via Michael addition polymerization. They have both ester groups and two kinds of hydrogen bond-forming groups (i.e., amide and secondary amino groups) and different flexible spacer length in the backbones. Such poly(ester-amide-secondary amine)s (PEAsAs) show low glass transition temperatures (Tg ≤ 18.4 °C), highly ordered smectic liquid crystalline phases, and reversible photoresponsivity. Their uniaxially oriented fibers fabricated via the melt spinning method exhibit good mechanical strength and photoinduced reversible bending/unbending and large stress at room temperature, which are largely influenced by the flexible spacer length of the polymers. Importantly, all these fibers can be easily reprogrammed under strain at 25 °C into stable fiber springs capable of showing a totally different photomobile mode (i.e., unwinding/winding), mainly owing to the presence of low Tg and both dynamic hydrogen bonding and stable crystalline domains (induced by the uniaxial drawing during the fiber formation). They can also be recycled from a solution at 25 °C. This work not only presents the first azo LCPs with 3D shape reprogrammability, recyclability, and photomobility at room temperature, but also provides some important knowledge of their structure-property relationship, which is useful for designing more advanced photodeformable azo polymers.

Do Aqueous Suspensions of Smectite Clays Form a Smectic Liquid-Crystalline Phase?

Bottom-up strategies for the production of well-defined nanostructures often rely on the self-assembly of anisotropic colloidal particles (nanowires and nanosheets). These building blocks can be obtained by delamination in a solvent of low-dimensionality crystallites. To optimize particle availability, determination of the delamination mechanism and the different organization stages of anisotropic particles in dispersion is essential. We address this fundamental issue by exploiting a recently developed system of fluorohectorite smectite clay mineral that delaminates in water, leading to colloidal dispersions of single-layer, very large (≈20 μm) clay sheets at high dilution. We show that when the clay crystallites are dispersed in water, they swell to form periodic one-dimensional stacks of fluorohectorite sheets with very low volume fraction (<1%) and therefore huge (≈100 nm) periods. Using optical microscopy and synchrotron X-ray scattering, we establish that these colloidal stacks bear strong similarities, yet subtle differences, with a smectic liquid-crystalline phase. Despite the high dilution, the colloidal stacks of sheets, called colloidal accordions, are extremely robust mechanically and can persist for years. Moreover, when subjected to AC electric fields, they rotate as solid bodies, which demonstrates their outstanding internal cohesion. Furthermore, our theoretical model captures the dependence of the stacking period on the dispersion concentration and ionic strength and explains, invoking the Donnan effect, why the colloidal accordions are kinetically stable over years and impervious to shear and Brownian motion. Because our model is not system specific, we expect that similar colloidal accordions frequently appear as an intermediate state during the delamination process of two-dimensional crystals in polar solvents.

Mixing‐Induced Orientational Ordering in Liquid‐Crystalline Organic Semiconductors

AbstractOrganic semiconductors (OSCs) often exhibit thermotropic liquid‐crystalline (LC) phases in which molecular orientational order is partially lost. The formation of a temporary LC state via a solution process is expected to promote printing‐based device production, although a method of controlling molecular ordering over LC states has not yet been developed. Here, it is demonstrated that long‐axis molecular ordering can be controlled under ambient conditions using unsymmetrically alkylated OSCs with high layered crystallinity. Introducing a small amount of OSC molecules with longer alkyl‐chain lengths leads to the conversion of the long‐axis disordered phase into a bilayer‐type ordered phase with improved hole mobility in the transistor characteristics. Analyses of the entropies of the transitions to the smectic LC phases at elevated temperatures demonstrate that the long‐axis molecular ordering can be driven by a balance between intralayer flip–flop motion and core–core interactions through LC phases. The proposed LC‐mediated solution processing paves the way toward high‐end printed electronics.

Synthesis and Liquid Crystalline Properties of Low Molecular Weight Bis- Chalcone Compounds.

In this paper, we report on the synthesis and liquid crystalline properties of some low molecular weight bis-chalcone compounds derived from acetone, cyclopentanone and cyclohexanone mesogenic cores. Structurally bis-chalcones belong to a broader family of chalcone compounds. Chalcone is a compound that consists of two aromatic rings linked by an unsaturated α, β-ketone. Liquid crystalline chalcones are prepared by aliphatic chain substituents on two aromatic rings. Chalcones are well studied for their mesomorphic properties. Compared to a large number of chalcone based LCs reported, only a few articles have been published on the mesomorphic properties of bis-chalcone compounds. The target compounds of the present study varied not only in their central core but also in number and position of terminal aliphatic chain substitution-a key structural unit in deciding the liquid crystalline properties of a compound. All target compounds were synthesized in good yield by base catalyzed Claisen-Schmidt condensation reaction. Molecular structures were confirmed by FT-IR, 1H NMR, 13C NMR, and mass spectroscopic methods. Liquid crystalline property of these compounds was evaluated using polarizing optical microscopy and differential scanning calorimetry. Although none of the acetone based compounds exhibited mesomorphism, cyclopentanone and cyclohexanone based compounds with octyloxy chain at para position on either side of the dibenzylidine ring stabilized liquid crystalline smectic (SmA and SmC) and nematic (N) phases. The observed structure-liquid crystalline property relationship was explained by structural analysis of molecules using DFT calculations. Considering the inherent photoluminescence nature of the chalcone moiety, a preliminary study was carried out on a selected compound to reveal its fluorescence property. Our study brings about an important structure-liquid crystalline property relationship in a relatively unexplored class of bis-chalcone liquid crystals.

The influence of neutral lipid composition on the physical properties and protein recruitment of lipid droplets

Lipid droplets are intracellular storage organelles for neutral lipids, such as triacylglycerols and sterol esters. They are surrounded by a phospholipid monolayer that embeds and associates with different proteins during the lipid droplet lifecycle. Recent experiments have shown that protein recruitment can change depending on the composition of the neutral core. Moreover, sterol-rich lipid droplets have been shown to undergo a phase change to an ordered liquid-crystalline smectic phase with concentric rings under the phospholipid monolayer.

Long-time relaxation dynamics in nematic and smectic liquid crystals of soft repulsive colloidal rods.

Understanding the relaxation dynamics of colloidal suspensions is crucial to identifying the elements that influence the mobility of their constituents, assessing their macroscopic response across the relevant time and length scales, and thus disclosing the fundamentals underpinning their exploitation in formulation engineering. In this work, we specifically assess the impact of long-ranged ordering on the relaxation dynamics of suspensions of soft repulsive rodlike particles, which are able to self-organize into nematic and smectic liquid-crystalline phases. Rods are modeled as soft repulsive spherocylinders with a length-to-diameter ratio L^{★}=5, interacting via the truncated and shifted Kihara potential. By performing dynamic Monte Carlo simulations, we analyze the effect of translational and orientational order on the diffusion of the rods along the relevant directions imposed by the morphology of the background phases. To provide a clear picture of the resulting dynamics, we assess its dependence on temperature, which can dramatically determine the response time of the system relaxation and the self-diffusion coefficients of the rods. The computation of the van Hove correlation functions allows us to identify the existence of rods that diffuse significantly faster than the average and whose concentration can be accurately adjusted by a suitable choice of temperature.

Volatility Transition from Short‐Term to Long‐Term Photonic Transistor Memory by Using Smectic Liquid Crystalline Molecules as a Floating Gate

AbstractRod‐like molecules with liquid crystalline phase transitions show highly ordered stacking and orientation, which is promising as the floating gate electret in high‐performance photonic field‐effect transistor (FET) memory. In this work, a series of rod‐like molecules, alkyl‐dinaphtho[2,3‐b:2′,3′‐f]thieno[3,2‐b]thiophene (Cn‐DNTT), are investigated with a smectic liquid crystalline phase transition. The photonic FET memory featuring these rod‐like molecules is correlated with their morphology and crystallographic properties. A volatility transition from short−term to long−term memory behavior is found by utilizing the smectic liquid crystalline phase transitions (SmX, X = H, K, E) to orient the stacking in the floating gate. Accordingly, the annealed 2,9‐didecyldinaphtho[2,3‐b:2′,3′‐f]thieno[3,2‐b]thiophene (C10‐DNTT) polycrystalline film with the optimized alkyl chain length achieved preferential end‐on orientation associated with the herringbone‐type stacking to store charges during photowriting, along with effective charge tunneling for the trapped charges during electrical erasing. Therefore, the resultant photonic FET memory provided a superior ON/OFF current ratio of up to 105 with retention of 104 after 104 s. The results demonstrate that rod‐like molecules with smectic liquid crystalline phase and highly ordered orientation have great potentials for developing high‐performance photonic FET memory.

Oxadiazolyl-Pyridinium as Cationic Scaffold for Fluorinated Ionic Liquid Crystals

The synthesis and characterization of a new class of 1,2,4-oxadiazolylpyridinium as a cationic scaffold for fluorinated ionic liquid crystals is herein described. A series of 12 fluorinated heterocyclic salts based on a 1,2,4-oxadiazole moiety, connected through its C(5) or C(3) to an N-alkylpyridinium unit and a perfluoroheptyl chain, differing in the length of the alkyl chain and counterions, has been synthesized. As counterions iodide, bromide and bis(trifluoromethane)sulfonimide have been considered. The synthesis, structure, and liquid crystalline properties of these compounds are discussed on the basis of the tuned structural variables. The thermotropic properties of this series of salts have been investigated by differential scanning calorimetry and polarized optical microscopy. The results showed the existence of an enantiotropic mesomorphic smectic liquid crystalline phase for six bis(trifluoromethane)sulfonimide salts.

Anhydrous Proton Transport within Phosphonic Acid Layers in Monodisperse Telechelic Polyethylenes

Polymers bearing phosphonic acid groups have been proposed as anhydrous proton-conducting membranes at elevated operating temperatures for applications in fuel cells. However, the synthesis of phosphonated polymers and the control over the nanostructure of such polymers is challenging. Here, we report the straightforward synthesis of phosphonic acid-terminated, long-chain aliphatic materials with precisely 26 and 48 carbon atoms (C26PA2 and C48PA2). These materials combine the structuring ability of monodisperse polyethylenes with the ability of phosphonic acid groups to form strong hydrogen-bonding networks. Anhydride formation is absent so that charge carrier loss by a condensation reaction is avoided even at elevated temperatures. Below the melting temperature (Tm), both materials exhibit a crystalline polyethylene backbone and a layered morphology with planar phosphonic acid aggregates separated by 29 and 55 Å for C26PA2 and C48PA2, respectively. Above Tm, the amorphous polyethylene (PE) segments coexist with the layered aggregates. This phenomenon is especially pronounced for the C26PA2 and is identified as a thermotropic smectic liquid crystalline phase. Under these conditions, an extraordinarily high correlation length (940 Å) along the layer normal is observed, demonstrating the strength of the hydrogen bond network formed by the phosphonic acid groups. The proton conductivity in both materials in the absence of water reaches 10-4 S/cm at 150 °C. These new precise phosphonic acid-based materials illustrate the importance of controlling the chemistry to form self-assembled nanoscale aggregates that facilitate rapid proton conductivity.

Photonic Bandgap in Achiral Liquid Crystals-A Twist on a Twist.

Achiral mesogenic molecules are shown to be able to spontaneously assemble into liquid crystalline smectic phases having either simple or double-helical structures. At the transition between these phases, the double-helical structure unwinds. As a consequence, in some temperature range, the pitch of the helix becomes comparable to the wavelength of visible light and the selective reflection of light in the visible range is observed. The photonic bandgap phenomenon is reported for achiral liquid crystals.

Ionic Liquid-Induced Phase-Separated Domains in Lipid Multilayers Probed by X-ray Scattering Studies.

A cellular membrane, primarily a lipid bilayer, surrounds the internal components of a biological cell from the external components. This self-assembled bilayer is known to be perturbed by ionic liquids (ILs) causing malfunctioning of a cellular organism. In the present study, surface-sensitive X-ray scattering techniques have been employed to understand this structural perturbation in a lipid multilayer system formed by a zwitterionic phospholipid, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine. The ammonium and phosphonium-based ILs with methanesulfonate anions are observed to induce phase-separated domains in the plane of a bilayer. The lamellar X-ray diffraction peaks suggest these domains to correlate across the bilayers in a smectic liquid crystalline phase. This induced IL-rich lamellar phase has a very low lamellar repeat distance, suggesting the formation of an interdigitated bilayer. The IL-poor phase closely related to the pristine lipid phase shows a decrement in the in-plane chain lattice parameters with a reduced tilt angle. The ammonium and phosphonium-based ILs with a relatively bulky anion, p-toluenemethanesulfonate, have shown a similar effect.

Synthesis and characterization of liquid crystalline epoxy resins to study the effect of mesogenic length on the physical properties

Two liquid crystalline epoxy (LCE) resins containing different mesogenic lengths were synthesized and cured with two different aromatic diamine curing agents, diaminodiphenylsulfone (DDS) and diaminodiphenylmethane (DDM) to prepare high performance LCE networks. The spectroscopic structures of LCE resins were identified by Fourier transform infrared (FT-IR) spectroscopy, Proton nuclear magnetic resonance (1H-NMR) spectroscopy, mass (MS) spectroscopy, and the formation of nematic and smectic liquid crystalline phase were observed by differential scanning calorimetry (DSC), and polarized optical microscopy (POM). The curing reactions and liquid crystalline textures of the LCE resins were also studied by DSC and POM on the process of curing. The thermal and mechanical properties were investigated for the cured LCE resins with different mesogenic lengths. These results show that the LCE cross-linked networks with long mesogenic group exhibited much higher storage modulus, glass transition temperature, thermal conductivity, thermal stability, and dimensional stability both in the regions of glassy and rubbery states. In addition, both LCE resins have superior thermal and mechanical properties compared to those of the commonly used epoxy resin.

Extraordinary magnetic field effects on the LC phases of homochiral and racemic 4-cyanoresorcinol-based diamagnetic bent-core mesogens

A huge effect of a magnetic field on the layer spacing of smectic and polar smectic liquid crystalline phases of a diamagnetic bent-core mesogen is reported, which is opposite for the uniformly chiral compound and its racemic mixture.