Liquid Crystal Mesophase Research Articles

Lamellar liquid crystals in commercial polyether‐modified polydimetilsiloxanes for coating applications: Structure, rheology and cross‐linking

AbstractWe have constructed the phase diagrams in water of two commercial additives for coatings consisting of polyether‐modified polydimethylsiloxanes. These aqueous systems form a liquid crystal mesophase (LC) at copolymer concentrations higher than 60 wt%. At low copolymer concentrations, this LC coexists with a diluted aqueous phase. Small angle x‐ray scattering (SAXS) measurements and polarized optical microscope observations indicate that the structure of the mesophase is lamellar, with an interlayer spacing that increases linearly with the concentration of water in the system. The lamellar liquid crystals display temperature‐dependent viscoelastic behavior, with the copolymer with longer spacing showing a much lower elastic modulus. Since one of the copolymer has terminal acryl groups, its lamellar phase can be crosslinked to produce gelled liquid crystals. Other cross‐linked self‐assembled structures, such as bicontinuous microemulsions, are envisaged.

Perylene-3,4,9,10-tetracarboxylic dianhydride dye intercalated liquid crystal molecules: Synthesis, spectroscopic characterizations and photoluminescence dynamics

The present research explores the interaction between perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA)-dye (PD) and 3b {(E)-1-[3-fluoro-4-(pentyloxy)phenyl]-2-(4-methylphenyl)diazene} liquid crystal (LC) mesophase, 3c{(E)-1-[3-fluoro-4-(hexyloxy)phenyl]-2-(4-methylphenyl)diazene} nematic liquid crystal (NLC) molecule. Spectroscopic characterizations of 3b@PD LC mesophase and 3c@PD NLC molecule were carried out using scanning electron microscopy (SEM), polarizing optical microscope (POM), Raman, Fourier transform infrared spectroscopy (FT-IR), and UV–visible analytical methods. The UV–visible studies revealed a red shift in absorption bands (348.0 nm to 374 nm) with a decrease in optical band gap from 2.43 eV to 2.25 eV. Room temperature photoluminescence (RTPL) spectra of 3b@PD LC mesophase exhibited blue light emission characteristics centred at 453.1 nm and 3c @PD NLC molecule showed broad emission peaks located at 400.7 nm and 324.8 nm. Steady-state photoluminescence (SSPL) spectra showcased indigo-purple emission bands corresponding to the wavelengths 303–353 nm, 420.5 nm, 418 nm, 418.3 nm, and 347.0 nm, however, for the 3c@PD NLC molecule, emission intensity peaks appeared at 429.6 nm, 418.0 nm and 329.0 nm. The stoke’s shift for 3b@PD LC mesophase varied between 0.01 eV to 0.613 eV while for 3c@PD NLC molecule it was found in between 0.317 eV to 0.453 eV. POM analysis unveiled distinct fan-like textures with varied colour interfaces. Time-resolved photoluminescence (TRPL) decay studies unveiled average lifetime of 3b@PD LC mesophase was 1.80 ns, 0.98 ns, 0.308 ns and for 3c@PD NLC molecule, the average lifetime was found to be 0.98 ns, 0.82 ns, and 0.306 ns at various excitation wavelengths. However, phosphorescence decay studies showed faster decay characteristics for 3c@PD NLC molecule (1.40 ns to 4.00 ns) compared with 3b@PD LC mesophase (1.65 to 5.42 ns) when excited at various wavelengths. The interaction between LC molecules and PTCDA demonstrated a significant enhancement in RTPL, TRPL, and SSPL properties, suggesting promising applications in photonics and optoelectronics.

Exceptional Alignment in a Donor–Acceptor Conjugated Polymer via a Previously Unobserved Liquid Crystal Mesophase

AbstractOrienting polymer semiconductors is desirable to optimize device characteristics, provide insight into microstructure, and magnify subtle phase behavior. Here, a combination of uniaxial strain and subsequent heating of the donor–acceptor (DA) polymer PBnDT‐FTAZ is discovered to lead to exceptional optical dichroic ratios of up to 38 (and close to 50 near the polymer's absorption edge). This alignment is achieved due to the existence of a previously undetected thermotropic liquid crystal (LC) mesophase. The LC transition, not discernable through calorimetry, is uncovered through a combination of in situ UV–vis spectroscopy, X‐ray scattering, and dynamic mechanical analysis (DMA). Comparing PBnDT‐FTAZ to the non‐fluorinated PBnDT‐HTAZ and the homo polymer PBnDT, all of which show similar thermal transitions, reveals that exceptional alignment is only found in PBnDT‐FTAZ. This is attributed to the PBnDT‐FTAZ film having two distinct liquid crystal populations, and the polymer templating to a highly aligned, high‐clearing temperature population when heated. The DMA thermal relaxation behavior observed here is also seen in other DA conjugated polymers suggesting that such thermotropic LC mesophases may be common in these materials. These findings demonstrate a polymer semiconductor with remarkable alignment and uncover phase behavior with broad implications for process‐structure‐property relationships in polymer semiconductors.

A Spectrally Programmable Liquid‐State Active System for High‐Performance (SPLASH) Multicolor Lasing and White Emission

AbstractThe development of a Spectrally Programmable Liquid‐State Active System for High‐performance (SPLASH) is introduced, which allows for multicolor lasing and White Emission. This completely liquid, three‐phase device showcases exceptional tunability within a singular Liquid Crystal Cell (LCC). Components include a Coumarin 540 (CM540)‐doped liquid crystal (LC) mesophase, an ionic liquid (RTIL) richly endowed with Rhodamine 6G (R6G) dye, and a Stilbene 420 (SB420)‐infused water‐based solution. This device displays significant accomplishments in multicolor tunability through the use of both lasing and fluorescence mechanisms. As a result, White Light Fluorescence (WFluo) and White Light Hybrid‐Emission (WHE) are showed, which consist of two lasing bands and one fluorescence. This is achieved in a liquid‐state environment characterized by phase separation and careful device management. Additionally, due to its fluid‐like nature and compact design, the device inherently offers considerable scalability — since its components can be easily adjusted and rearranged. This approach promises ground‐breaking advancements in high‐impact applications such as the Li‐Fi concept. Therefore, SPLASH stands out as an innovative platform for White Light Fluorescence (WFluo) and Multicolor Lasing (ML) within liquid‐state active systems.

Bio-inspired liquid crystal gel induction via nano-hydroxyapatite mesogens: Viscoelastic and hemostasis regulation under bone remodeling pH and temperature control

In this work, a liquid crystal mesophase as a potential bone-repairing booster has been induced from a polyacrylic acid (PAAc) gel loaded with synthetic hydroxyapatite nanoparticles (nHA) under physiological conditions of pH and temperature that resemble the early stages of bone formation. Dynamic processes at the microscale in biological systems require a material capable of behaving following a specific order and fluency. Besides, they must fulfill conditions such as biocompatibility and good mechanical properties. Our study aimed to obtain new data about the safety, hemostasis, biocompatibility (activated partial thromboplastin time (APTT) test, prothrombin time (PT) test, lactate dehydrogenase (LDH) test, red blood cell morphology observation, hemolysis percentage) and physicochemical/mechanical behavior (Attenuated Total Reflection (ATR), Infrared spectroscopy and rheological assays) of nanoparticles, and materials built with them. Both systems have shown biocompatibility with red blood cells and adequate flow properties, demonstrating promising qualities for applicability. The formation of lyotropic liquid crystals at physiological conditions was evaluated with crossed polaroids microscope with a temperature control plate. The formation of these structures under bone remodeling conditions shows the potential application of PAAc-nHA materials. In literature, the study of materials applied as bone fillers is mainly focused on mechanical and osteoblasts compatibility assays. However, the hematological effect, consequences on the coagulation cascade, the integrity of cell membranes, and hemolysis percentage have not been addressed thoroughly. The strength of our work is focused on considering these aspects when tridimensional arrangements essential for bone formation are formed.

Optical Biosensing of Polarized Light

Interactions between liquid crystal molecules and target analytes open up various biosensing applications for quick screening and point-of-care applications. In this review, we categorized biosensors by type, depending on the liquid crystal mesophase, and considered several applications for the detection of biomolecules, point-of-care diagnostics and environmental monitoring. We also discuss interactions between polarized light and target pathogens dispersed in biological fluids, which result in the change of the polarization state. An array of the Stokes parameters can be compared with the pattern, and a proper pathogen can be manifested. We suggest that a combination of a micropolarizer array and a complementary metal oxide semiconductor sensor is an optimal setup for the detection of pathogens. Herein, we discuss the working principles of liquid crystal biosensors and their fabrication principles. In addition, relevant theoretical and practical issues related to liquid crystal biosensors are outlined. In general, this review gives an in-depth survey of the research on liquid crystal-based sensors, making it easier for researchers to locate their niche and make contributions to this subject from multiple viewpoints.

Impact of Molecular-level Structural Disruption on Relaxation Dynamics of Polymers with End-on and Side-on Liquid Crystal Moieties.

In side-chain liquid crystal polymers (SCLCPs), short side chains are attached on a flexible polymer backbone, and each side chain can have a liquid crystal (LC) group attached at the final bead in either an end-on or a side-on configuration. SCLCPs with random sequences of end-on and side-on LC moieties exhibit nonmonotonic thermal behavior as a function of composition, with some mixed sequences having a lower isotropic to LC phase transition than either purely end-on or side-on configurations. The origin of this nonmonotonic thermal trend lies in the disruption of molecular-level positional ordering and alignment due to the different preferred types of ordering of the different LC attachment types. We compare coarse-grained molecular dynamics (MD) simulations and experiments on SCLCP systems with only one type of LC moiety and demonstrate qualitative agreement in the observed mesophases of end-on and side-on SCLCP systems. Specifically, end-on SCLCPs display a smectic B-like mesophase, with layers of polymer between LC layers, while side-on SCLCPs exhibit a quasi-hexagonal columnar structure of polymer and a nematic surrounding the LC mesophase. Detailed analysis of SCLCP systems with various compositions of these types of LC attachments via MD reveals structural disruption in systems with intermediate compositions. Simulation snapshots and anisotropy ratio measurements show how random SCLCP systems deviate from the expected behavior of prolate or oblate systems in terms of their conformation. This molecular disruption in random SCLCP systems, particularly with a high composition of side-on LC moieties, also significantly impacts the relaxation dynamics. Modifying the composition of the LC type of attachment (molecular structure) is a possible route to tuning both the phase behavior and mechanical response of these systems.

Subtle Molecular Changes Largely Modulate Chiral Helical Assemblies of Achiral Conjugated Polymers by Tuning Solution-State Aggregation.

Understanding the solution-state aggregate structure and the consequent hierarchical assembly of conjugated polymers is crucial for controlling multiscale morphologies during solid thin-film deposition and the resultant electronic properties. However, it remains challenging to comprehend detailed solution aggregate structures of conjugated polymers, let alone their chiral assembly due to the complex aggregation behavior. Herein, we present solution-state aggregate structures and their impact on hierarchical chiral helical assembly using an achiral diketopyrrolopyrrole-quaterthiophene (DPP-T4) copolymer and its two close structural analogues wherein the bithiophene is functionalized with methyl groups (DPP-T2M2) or fluorine atoms (DPP-T2F2). Combining in-depth small-angle X-ray scattering analysis with various microscopic solution imaging techniques, we find distinct aggregate in each DPP solution: (i) semicrystalline 1D fiber aggregates of DPP-T2F2 with a strongly bound internal structure, (ii) semicrystalline 1D fiber aggregates of DPP-T2M2 with a weakly bound internal structure, and (iii) highly crystalline 2D sheet aggregates of DPP-T4. These nanoscopic aggregates develop into lyotropic chiral helical liquid crystal (LC) mesophases at high solution concentrations. Intriguingly, the dimensionality of solution aggregates largely modulates hierarchical chiral helical pitches across nanoscopic to micrometer scales, with the more rigid 2D sheet aggregate of DPP-T4 creating much larger pitch length than the more flexible 1D fiber aggregates. Combining relatively small helical pitch with long-range order, the striped twist-bent mesophase of DPP-T2F2 composed of highly ordered, more rigid 1D fiber aggregate exhibits an anisotropic dissymmetry factor (g-factor) as high as 0.09. This study can be a prominent addition to our knowledge on a solution-state hierarchical assembly of conjugated polymers and, in particular, chiral helical assembly of achiral organic semiconductors that can catalyze an emerging field of chiral (opto)electronics.

Novel star-shaped liquid crystal macromolecules based on conjugated structures of azo and Schiff bases: synthesis and properties

ABSTRACT In this paper, a series of novel liquid crystal units (ASE-n, n = 4, 6, 8) of azo Schiff bases with sulphonic acid (-SO3H) as terminal substituents and different alkyl chain lengths were designed and synthesised. Nine star-shaped liquid crystal macromolecules with different central groups (ASE-P-n, ASE-T-n, ASE-G-n, n = 4, 6, 8) were synthesised by esterification of three novel azo Schiff base liquid crystal units (ASE-n, n = 4, 6, 8) with phloroglucinol, pentaerythritol and glucose. The structure of the synthesised compounds were analysed by infrared spectroscopy and 1H NMR. The results showed that all the compounds were consistent with the molecular structure design. The properties of liquid crystal such as phase transition temperature and liquid crystal mesophase range were characterised by POM and DSC. The effects of alkyl chain length and branched degree on the properties of liquid crystal were studied. The maximum absorption spectrum of the compound was determined by UV-Vis spectrophotometry. The photoisomerisation reaction of the compound was also studied. Under ultraviolet light (λ = 365 nm) irradiation, the effect of different duration on the cis-absorption percentage of azo (-N=N-) bond in the compound was studied.

Effect of doping ferroelectric BaTiO3 nanoparticles on dielectric, electro-optical, and ionic properties of antiferroelectric bent-core liquid crystal

Nano-doping in polar bent-core liquid crystals is the topic of current interest for designing multifunctional smart materials. Here, we study the effect of doping of two different-sized (5–15 nm and 50–70 nm) ferroelectric BaTiO3 nanoparticles on the dielectric, electro-optical and ionic properties of antiferroelectric smectic A bent-core liquid crystal. Doping with both the sizes of nanoparticles results in lowering of the transition temperature of the liquid crystal mesophases. Both, the pure as well as doped samples show a soft mode in their antiferroelectric smectic A phase. In comparison to pure liquid crystal, the dielectric strength of the soft mode in doped samples is decreased, while their relaxation frequencies show an increasing behavior. Additionally, a decrement has been observed in the spontaneous polarization of the doped samples. A drop in polarization as well as soft mode dielectric strength values in doped samples, simultaneously point to an antiparallel dipole–dipole correlation between the ferroelectric nanoparticles and antiferroelectric liquid crystal molecules. Higher values of molecular mode relaxation frequencies obtained in nano-doped samples indicate a decrement in viscosity and dilution of pure liquid crystal. An important electro-optical parameter, the response time shows a remarkable decrement for the higher size (50–70 nm) nanoparticles doped sample. An enhancement in direct current conductivity and ion diffusion coefficient is observed for both the nano-doped samples. The smaller size (5–15 nm) ferroelectric nanoparticles reduce the mobile ion concentration and act as ion-capturing agents for the liquid crystal. A systematic investigation of the nano-doped bent-core liquid crystal can catalyze the use of the combined media for faster switching electro-optic applications.

Synthesis and characterisation of novel aromatic ester swallow-tailed cholesteric liquid crystal polymers

ABSTRACT In this paper, two novel aromatic ester swallow-tailed liquid crystal monomers M1 and M2 and a straight chain cholesteric liquid crystal monomer M3 were designed and synthesised. Two series of liquid crystal polymers, P1 series and P2 series, were graft-copolymerised with M and polymethylhydrosiloxane (PHMS). All the synthesised liquid crystal monomers and polymers were characterised by IR and 1H NMR and confirmed to the predicted molecular structure. The liquid crystal and thermal properties of the synthesised compounds were tested by DSC, POM, TGA and optical rotation. The results show that the monomer M1 is a monotropic nematic liquid crystal, and the Schlieren texture appears during the cooling process. M2 is an enantiotropic nematic liquid crystal with filamentous and schlieren texture. M3 is a thermotropic enantiotropic cholesteric phase with oily streak and focal cone texture. Both polymers P1 and P2 show typical Grand-Jean texture, and with the increase of monomer M3 content, the polymer clearing point temperature Ti increases continuously, the liquid crystal mesophase range widens, and the specific rotation value increases.

Fullerene-doped polyimide materials treated via the vacuum ultraviolet irradiation: Novel possible approach to create the structured relief

<p>Among the various surface reliefs obtained by the modification of the nanostructured materials used for the orientation of the liquid crystal molecules or applied as the possible way to extend the optical limiting mechanisms, the vacuum ultraviolet irradiation can provoke the novel approach with the varied contact angle and can be recommended for use in the development of the light- and electro-addressable liquid crystal spatial light modulators, switchers, and limiters. The main accent in the current paper is connected with the study of an impact of the vacuum ultraviolet irradiation with the different wavelength and power densities on the fullerene-structured polyimide thin films. To support the proposed idea, the spectral measurements were carried out, the contact wetting angles of the structured surface were determined, and an atomic force microscopic analysis was performed. Based on the data obtained, it is proposed to effectively use such relief formed by the vacuum ultraviolet irradiation for the design of the modulators and converters of the laser radiation, some biomedicine devices and the solar cells as well where a liquid crystal mesophase is actively used as an electro-optical modulating layer. Some ideology of the current article is aimed that the polyimide materials, when irradiated in the vacuum ultraviolet, can perform a dual role, as a photo layer and as an orienting layer as well.</p>

Effect of molecular aspect ratio on structure, dynamics and phase stability of thermotropic liquid crystals studied by molecular dynamics simulation

Due to the importance of liquid crystals in modern technology and food industry, understanding their structural and dynamical properties are scientifically important. In this study, we applied extensive molecular dynamics simulations to infer the effect of the molecular elongation on the formation, stability and dynamics of liquid crystal mesophases in a system of Gay-Berne model mesogens with parameters GB (k,k′=20,μ=1,ν=1). Four aspect ratio values, k=2,3,4.4 and 5, were studied at pressure P*=4. Thermodynamics properties, the order parameter and pair distribution functions (both translational and positional), helped to identify phases, hysteresis, and consequently phase diagrams. By increasing aspect ratio from 2 to 5, nematic and smectic phases were induced and all transition temperatures were shifted to higher values, hence, the range of stability of the nematic and smectic mesophases became wider. The analysis of the coordination numbers and angular distribution functions showed that the structure of the solid phase of system with k=2 at lowest temperatures was fcc which by increasing the aspect ratio changed to a complete hexagonal in-layer structure. Moreover, by increasing the axial ratio of particles, decoupling between the principal components of diffusion coefficients increased, where it reflects an increase in the molecular orientational order in the system with higher k. The effect of increasing aspect ratio was more pronounced on inter-layers diffusion rather than the in-layers. In all mesophases parallel components of diffusion coefficients were greater than the perpendicular components. We analyzed the results based on the existing theoretical descriptions and experimental observations.

Lyotropic liquid crystal mesophases as transdermal delivery systems for lipophilic drugs: A comparative study

The present work aimed to evaluate different Liquid Crystal Mesophases (LCM) as transdermal drug delivery systems (TDDS) for nifedipine (NFD), a lipophilic drug model. The formulations composed of water, Citrus sinensis essential oil (CSEO), PPG-5-CETETH-20, and Olive oil ester PEG-7 were obtained and characterized by polarized light microscopy (PLM), rheology, small-angle x-ray scattering (SAXS), Fourier transform infrared coupled with an attenuated total reflection accessory (FTIR-ATR) and in vitro assays: bioadhesion, drug release, skin permeation, and retention tests. As a result, changes in component proportions led to several transparent viscous systems with an anisotropic profile. PLM and SAXS proved the presence of lamellar (S1), hexagonal (S3), and lamellar + hexagonal (S2) LCM, and rheology showed a high viscoelasticity profile. LCMs were able to adhere to the skin, and S2 achieved higher adhesion strength. NFD (5 mg/mL) has not modified the organization of LCMs. Results also showed that S3 promoted higher permeation and retention and higher disorganization of stratum corneum lipids, which is the main permeation-enhancing mechanism. Thus, the formulations obtained can carry and improve drug delivery through the skin and are promising TDDS for lipophilic drug administration, such as NFD.

Control of the Organization of 4,4′-bis(carbazole)-1,1′-biphenyl (CBP) Molecular Materials through Siloxane Functionalization

We show that through the introduction of short dimethylsiloxane chains, it was possible to suppress the crystalline state of CBP in favor of various types of organization, transitioning from a soft crystal to a fluid liquid crystal mesophase, then to a liquid state. Characterized by X-ray scattering, all organizations reveal a similar layered configuration in which layers of edge-on lying CBP cores alternate with siloxane. The difference between all CBP organizations essentially lay on the regularity of the molecular packing that modulates the interactions of neighboring conjugated cores. As a result, the materials show quite different thin film absorption and emission properties, which could be correlated to the features of the chemical architectures and the molecular organizations.

Light-induced bi-directional switching of thermal conductivity in azobenzene-doped liquid crystal mesophases.

The development of systems that can be switched between states with different thermal conductivities is one of the current challenges in materials science. Despite their enormous diversity and chemical richness, molecular materials have been only scarcely explored in this regard. Here, we report a reversible, light-triggered thermal conductivity switching of ≈30-40% in mesophases of pure 4,4'-dialkyloxy-3-methylazobenzene. By doping a liquid crystal matrix with the azobenzene molecules, reversible and bidirectional switching of the thermal conductivity can be achieved by UV/Vis-light irradiation. Given the enormous variety of photoactive molecules and chemically compatible liquid crystal mesophases, this approach opens unforeseen possibilities for developing effective thermal switches based on molecular materials.

π-Electronic ion pairs: building blocks for supramolecular nanoarchitectonics viaiπ-iπ interactions.

The pairing of charged π-electronic systems and their ordered arrangement have been achieved by iπ-iπ interactions that are derived from synergetically worked electrostatic and dispersion forces. Charged π-electronic systems that provide ion pairs as building blocks for assemblies have been prepared by diverse strategies for introducing charge in the core π-electronic systems. One method to prepare charged π-electronic systems is the use of covalent bonding that makes π-electronic ions and valence-mismatched metal complexes as well as protonated and deprotonated states. Noncovalent ion complexation is another method used to create π-electronic ions, particularly for anion binding, producing negatively charged π-electronic systems. Charged π-electronic systems afford various ion pairs, consisting of both cationic and anionic π-systems, depending on their combinations. Geometries and electronic states of the constituents in π-electronic ion pairs affect the photophysical properties and assembling modes. Recent progress in π-electronic ion pairs has revealed intriguing characteristics, including the transformation into radical pairs through electron transfer and the magnetic properties influenced by the countercations. Furthermore, the assembly states exhibit diversity as observed in crystals and soft materials including liquid-crystal mesophases. While the chemistry of ion pairs (salts) is well-established, the field of π-electronic ion pairs is relatively new; however, it holds great promise for future applications in novel materials and devices.

Magnetocontrollable droplet mobility on liquid crystal-infused porous surfaces.

Supplementary material (further details of the stability of LCIPS against water-induced dewetting, the interfacial tension and contact angle measurement using a goniometer, the estimation of the thickness of LC wrapping layer at air-water interface on droplets, SEM measurements, the average sliding velocity of a water droplet on 5CB, E7, silicone oil, and mineral oil films with and without a magnetic field, representative force diagram (Fd versus time) of a 3-µL water droplet moving at a speed of 0.1 mm/s on a nematic 8CB film, Fdynamic acting on 3 µL water droplets moving at speeds of 0.1-1 mm/s on an isotropic 8CB film, the calculated magnetic coherence length as a function of the magnitude of the magnetic field applied to the nematic LCIPS, and the apparent advancing and receding contact angles of a moving water droplet on nematic LCIPS as a function of time, and polarized light micrographs (top view) of a nematic 8CB film between two DMOAP-functionalized glass slides before and after applying a horizontal magnetic field) is available in the online version of this article at 10.1007/s12274-022-5318-y.

Poly(ionic liquid) membranes preserving liquid crystalline microstructures for lithium-ion enrichment

The combination of membrane separation technology and hydrometallurgy has opened up new possibilities for the recovery and recycling of lithium from ever-growing spent lithium-ion batteries. Herein, we prepared a series of positively charged poly(ionic liquid) membranes preserving liquid crystal mesophases and investigated the monatomic ion separation capacity of the liquid crystalline membranes by diffusion dialysis experiments using the simulative spent battery leachate. The results revealed that liquid crystalline membranes with bicontinuous cubic liquid crystal structure possessed great potential as precise ion separation membranes for lithium-ion enrichment. Compared to the other topological structures, the bicontinuous cubic liquid crystal structure enhanced both the Li+ flux and ion selectivity of the membranes. The ion flux of the membrane with this structure was three times higher than that of amorphous membranes. Meanwhile, the Li+/Ni2+ selectivity was up to 7.40, which was significantly higher than that of hexagonal liquid crystalline membranes (2.59) and commercial membranes AMI-7001S (5.71). Moreover, the preservation of liquid crystal structures obviously improved the water management capacity and mechanical strength of the membranes.

Effect of disubstitution pattern of the terminal alkyl chains on the mesophase of liquid crystals based on lanthanide(III) complexes: A study of the thermal, emission and dielectric behavior

In the present work, new luminescent lanthanide complexes with extended mesomorphic range were prepared by coordination to lanthanide ions (Eu3+, Sm3+ and Tb3+) of the new 4-pyridone based organic ligands (L) with 3,4- (7-n) and 3,5-di(alkyloxy)benzyl (8-n) mesogenic groups and variable length (n = 12 or 14 carbon atoms) onto the benzyl unit. The cumulative results of the elemental analyses as well as the 1H, 13C NMR and IR spectroscopies support the structure of the organic derivatives and their lanthanide complexes [LnL3(NO3)3] (9-n/Ln and 10-n/Ln) described in this work. These complexes show characteristic lanthanide solid state emission, both at room and elevated temperatures corresponding to crystalline, glassy or liquid crystal states. The long range SmA phases displayed by all complexes were supported by a combination of characterization methods, including: differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and variable-temperature powder X-ray diffraction (XRD). This work shows that the number, substitution pattern and length of flexible alkoxy chains are important parameters to control the phase-transition characteristics of the lanthanide complexes. Complexes with 3,4-disubstituted pattern (9-n/Ln) show higher clearing temperatures (nearly 60 °C for Eu3+, 70 °C for Sm3+ and 85 °C for Tb3+ complexes) compared to their counterparts with 3,5-disubstituted pattern (10-n/Ln). Moreover, complexes 9-n/Ln crystallize when cooling their LC phase while complexes 10-n/Ln are stable in glassy state at room temperature as a consequence of the different close interdigitated molecular packing evidenced by XRD measurements. Dielectric spectroscopy was employed to detect the changes of order degree specific to each phases (crystalline, LC or isotropic). The variation of dielectric constant and the electrical conductivity versus temperature shows three transition intervals for selected complexes 10-14/Sm and 10-14/Tb, which delimit the main intervals: 45–60 °C, 90–110 °C; 140–160 °C corresponding to the Cr1-Cr2, Cr2 – SmA and SmA-Iso transitions, and agree very well with the DSC results. The change of characteristic time, obtained by Havriliak-Negami fit function, with temperature also provides a very good correlation with the DSC and POM results.