Search Results (28)

We develop a theoretical model for the flexoelectric instability in bent-core nematic liquid crystals, focusing on the coupling between elastic distortions and an external electric field through flexoelectric polarization. The analysis is carried out in the nematic phase close to the twist-bend transition, where both the flexoelectric coefficients and the effective bend elastic constant exhibit strong temperature dependence. Within a Landau–de Gennes framework, we derive analytical expressions for the threshold electric field and the corresponding wave vector of the emerging periodic modulation by minimizing the total free energy and assuming $K_1=K_2$. Numerical simulations illustrate the temperature dependence of the threshold parameters and the role of dielectric anisotropy and elastic constants. The results indicate that the flexoelectric instability may occur only within a finite temperature interval above the transition into the twist-bend phase and that both the threshold electric field and the periodic structure’s wave vector decrease as the temperature decreases. Full article

Phosphorus is an indispensable key element in life systems and materials science. Here in this work, several cyanoterphenyl-based phosphinic acid-bridged liquid crystal (LC) dimers of 2(CTOn)P (n = 6, 11) and their methyl esterification derivatives of 2(CTOn)P1E have been synthesized through hydrophosphination reaction followed by Suzuki coupling. The cyanoterphenyl LC dimers of 2(CTOn)P and methyl esterified 2(CTOn)P1E exhibit rich enantiotropic LC mesophases such as nematic (N), smectic A (SmA) and highly ordered smectic E (SmE), rather than the monotropic N or twist bend nematic (N_TB) displayed by the analogous phosphinic acid-bridged cyanobiphenyl LC dimers of 2(CBOn)P as reported previously. The phase transition temperatures of the cyanoterphenyl LC dimers 2(CTOn)P are also significantly higher than those of the cyanobiphenyl series, which is attributed to the larger π-conjugated system of cyanoterphenyl as compared with cyanobiphenyl, resulting in much enhanced π-π stacking interactions. However, the significantly enhanced interactions also make them extremely insoluble; thus, a different two-step synthesis pathway combining hydrophosphination with Suzuki coupling reactions was adopted. It is worth pointing out that by combining multiple characterization techniques, including DEPT 135°, ¹³C NMR, and HR-MS spectra, the definite molecular composition and structure of a byproduct with a third pro-mesogen attached via a branching alkyl spacer has been unambiguously demonstrated, which evidently deepens our understanding of the free radical-mediated hydrophosphination reaction mechanism, thereby providing valuable guidance for diminishing side reactions and achieving well-preparation of the high-purity phosphorus-containing LC dimers. Such phosphinic acid functionalized LC materials are envisioned to bear some unique application prospects. Full article

We report the first examples of bent-shaped LC dimers based on a seven-membered bridged stilbene. We synthesized nonylene- and ether-linked cyano-terminated dimers (sC9-tCN and sOC7O-tCN, respectively) and a homologous series of nonylene-linked alkyl-terminated dimers (sC9-tCn) with alkyl carbon atoms n = 1–6. Polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction measurement were employed to investigate the phase-transition behavior and LC phase structures. sC9-tCN and sOC7O-tCN only exhibited a nematic (N) phase, whereas sC9-tCn (n = 1–5) formed both the N_TB and N phases. sC9-tC5 additionally formed an unidentified X phase from the N_TB phase and sC9-tC6 exhibited a smectic A phase from the N phase. The weak dispersion force and intermolecular affinity provided by the terminal alkyl chains are likely to be preferable to the large dipole–dipole interactions by the cyano termini for the N_TB phase formation of the present dimers. The isotropic points of sC9-tCn showed an odd–even oscillation with n, whereas the N–N_TB phase transition temperatures were comparable. Remarkably, the N_TB stripe textures of sC9-tCn appeared perpendicular to the rubbing direction, and the N–N_TB phase transitions exhibited their second-order nature. This study revealed the unique N_TB phase properties of the 7-membered bridged stilbene-based LC dimers. Full article

Bent-shaped liquid crystal (LC) dimers, trimers, and oligomers are intriguing because of their unique liquid crystallinities, which have gained further impetus after the identification of the twist-bend nematic (N_TB) phase in these molecules. LC trimers exhibiting the N_TB phase still remain relatively rare compared to the predominant LC dimers. We report the first homologs of selenium-linked LC trimers, 4,4′-bis[ω-(4-cyanobiphenyl-4′-ylseleno)alkoxy]biphenyls (CBSenOBOnSeCB) with carbon numbers in the alkyl-chain spacers, n = 7 or 9). Polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction (XRD) measurements were performed to investigate the phase transition behavior and mesophase structures of the trimers. Both CBSenOBOnSeCB trimers exhibited nematic (N) and N_TB phases. The XRD measurements revealed the presence of smectic A-like cybotactic clusters with a triply intercalated structure in the N and N_TB phases. The LC phase transition temperatures of CBSenOBOnSeCB were lower than those of the already-known ether-linked CBOnOBOnOCB and thioether-linked CBSnOBOnSCB counterparts. This trend is ascribed to the enhanced molecular bending and molecular flexibility of CBSenOBOnSeCB, which are caused by the smaller bond angle and greater bond flexibility of C–Se–C compared to C–O–C and C–S–C. This study offers a new molecular design for multiply linked LC oligomers with heavier chalcogen atoms. Full article

In this study, we employed density functional theory (DFT), a standard method in quantum chemistry, to investigate the structural intricacies of thioether-linked naphthalene-based liquid-crystal dimers. The theoretical analysis included the calculation of the molecular bend angle, a crucial factor influencing the formation of the twist–bend nematic (N_TB) phase, as well as other molecular parameters such as transition dipole moments, bond lengths, and bond energies. These calculations allowed for the determination of the probable conformations and the computation of their vibrational spectra, which are essential for interpreting experimental spectra. Connecting these insights, we identified stable conformations and observed differences in the spectra between the conventional nematic (N) and N_TB phases. The combined DFT calculations and infrared absorbance measurements allowed us to investigate the structure and intermolecular interactions of molecules in the N and N_TB phases of the dimers. Notably, significant changes in average absorbance were detected in the experimental spectra in the N_TB phase. During the transition from the N phase to the N_TB phase, a clear decrease in absorbance for longitudinal dipoles and an increase for transverse dipoles were observed. This phenomenon suggests that longitudinal dipoles are antiparallel, while transverse dipoles are parallel. To verify the influence of nearest-neighbor interactions, DFT calculations were conducted on a system comprising several neighboring molecules. Full article

We report the first homologous series of methylene-linked cyanobiphenyl- and cyanoterphenyl-based liquid crystal (LC) dimers (CBnCT). To induce the heliconical twist-bend nematic (N_TB) phase through bent molecular shapes, the CBnCT homologs have an odd-numbered flexible alkylene spacer (n) ranging from 1 to 17. Polarized optical microscopy and differential scanning calorimetry are used to identify phases and analyze the phase-transition behavior. Except for n = 1, all the CBnCT homologs exhibit the conventional nematic (N) and N_TB phases. The CBnCT dimers with n = 3 and 5 show a monotropic N_TB phase, while those with n = 7, 9, 11, 13, 15, and 17 demonstrate an enantiotropic N_TB phase below the conventional N phase temperature. The N_TB phases of the CBnCT dimers (n = 7, 9, and 11) remain stable down to room temperature and vitrify without crystallization. Compared with cyanobiphenyl-based LC dimer homologs (CBnCB), the CBnCT dimers show significantly broader N and N_TB phase temperature ranges with higher isotropic and N_TB–N phase-transition temperatures. The N_TB phase temperature ranges of CBnCT (n = 7, 9, 11, and 13) are over 100 °C. Additionally, more CBnCT homologs exhibit the enantiotropic N_TB phase than the CBnCB ones. These enhancements result from increased π-conjugation and asymmetric molecular structures. Furthermore, CB9CT exhibits higher birefringence than CB9CB owing to its longer π-conjugated terphenyl moiety. Full article

Liquid crystal (LC) droplets are highly attractive for applications in privacy windows, optical switches, optical vortices, optical microresonators, microlenses, and biosensors due to their ease of fabrication and easy alignment at surfaces. This review presents the latest advancements in LC droplets, which have nematic, chiral nematic, and twist–bend nematic and ferroelectric nematic phases, or blue phases. Finally, it discusses the challenges and opportunities for applications based on LC droplets. The main challenges encompass the precise control of internal structures and defects to meet diverse application requirements, enhancing stability and durability across various environments, reducing large-scale production costs to improve commercial feasibility, increasing response speeds to external stimuli to adapt to rapidly changing scenarios, and developing tunable LC droplets to achieve broader functionalities. Full article

This work aims to determine how the nematic twist-bend phase (N_TB) of bismesogens containing two rigid parts of cyanobiphenyls connected with a linking chain containing n = 7, 9, and 11 methylene groups behaves in mixtures with structurally similar cyanobiphenyls nCB, n = 4–12, 14. The whole phase diagrams are presented for the CB7CB-nCB system. For the other systems, CB9CB-nCB and CB11CB-nCB, only curves corresponding to N_TB-N phase transition are presented. Based on the temperature-concentration range of the existence of N_TB phase, it was established that an increase in the alkyl chain length of CBnCB causes an increase in the stability of the N_TB phase. But surprisingly, an increase in the alkyl chain length of nCB compounds does not change the slope of the N_TB-N equilibrium line on phase diagrams. It is slightly bigger when the nCB compound has the same length of alkyl chain as the length of the linking group of a bismesogen. XRD studies were carried out for two mixtures. Full article

Photoisomerizable molecules in liquid crystals (LCs) allow for photoinduced phase transitions, facilitating applications in a wide variety of photoresponsive materials. In contrast to the widely investigated azobenzene structure, research on the photoinduced phase-transition behavior of imine-based LCs is considerably limited. We herein report the thermal and photoinduced phase-transition behaviors of photoisomerizable imine-based LC dimers with twist–bend nematic (N_TB) phases. We synthesize two homologous series of ester- and thioether-linked N-(4-cyanobenzylidene)aniline-based bent-shaped LC dimers with an even number of carbon atoms (n = 2, 4, 6, 8, and 10) in the central alkylene spacers, namely, CBCOOnSBA(CN) and CBOCOnSBA(CN), possessing oppositely directed ester linkages, C=OO and OC=O, respectively. Their thermal phase-transition behavior is examined using polarizing optical microscopy and differential scanning calorimetry. All dimers form a monotropic N_TB phase below the temperature of the conventional nematic (N) phase upon cooling. Remarkably, the N_TB phases of CBCOOnSBA(CN) (n = 2, 4, 6, and 8) and CBOCOnSBA(CN) (n = 6 and 8) supercool to room temperature and vitrify without crystallization. In addition, the phase-transition temperatures and entropy changes of CBCOOnSBA(CN) are lower than those of CBOCOnSBA(CN) at the same n. Under UV light irradiation, the N_TB and N phases transition to the N and isotropic phases, respectively, and reversibly return to their initial LC phases when the UV light is turned off. Full article

The twist-bend nematic liquid crystal phase is a three-dimensional fluid in which achiral bent molecules spontaneously form an orientationally ordered, macroscopically chiral, heliconical winding of a ten nanometer-scale pitch in the absence of positional ordering. Here, the structure of the twist-bend phase of the bent dimer CB7CB and its mixtures with 5CB is characterized, revealing a hidden invariance of the self-assembly of the twist-bend structure of CB7CB, such that over a wide range of concentrations and temperatures, the helix pitch and cone angle change as if the ground state for a pitch of the TB helix is an inextensible heliconical ribbon along the contour formed by following the local molecular long axis (the director). Remarkably, the distance along the length for a single turn of this helix is given by 2πR_mol, where R_mol is the radius of bend curvature of a single all-trans CB7CB molecule. This relationship emerges from frustrated steric packing due to the bent molecular shape: space in the fluid that is hard to fill attracts the most flexible molecular subcomponents, a theme of nanosegregation that generates self-assembled, oligomer-like correlations of interlocking bent molecules in the form of a brickwork-like tiling of pairs of molecular strands into duplex double-helical chains. At higher temperatures in the twist-bend phase, the cone angle is small, the director contour is nearly along the helix axis z, and the duplex chains are sequences of biaxial elements formed by overlapping half-molecule pairs, with an approximately 45° rotation of the biaxis between each such element along the chain. Full article

The second, lower-temperature nematic phase observed in nonlinear dimer liquid crystals has properties originating from nanoscale, polar, intermolecular packing preferences. It fits the description of a new liquid crystal phase discovered by Vanakaras and Photinos, called the polar-twisted nematic. It is unrelated to Meyer’s twist-bend nematic, a meta-structure having a macroscale director topology consistent with Frank–Oseen elastic theory. Full article

A new mesogenic non-symmetric dimeric monomer with a terminal olefin function, forming a twist bend nematic (N_tb) as well as a nematic (N) phase, was synthesized, using an enhanced synthetic methodology, which avoids isomerization of the terminal double bond in the preparation of the dimer. This monomer was attached to a pentamethyldisiloxane group, resulting in the SmA LC phase behavior of the ensuing material. Linking the monomer to a siloxane main chain resulted in nematic phase behavior. Detailed studies with the N_tb phase forming dimer DTC5C7 show full miscibility of the dimer and the new LC polymer in the LC state, suggesting that the side-chain LC polymer forms a N_tb phase as the low-temperature nematic phase. Copolymerizing the monomer with a cyanobiphenyl-based monomer allows us to tune the glass transition and phase behavior further. Full article

The formation of the nematic to twist-bend nematic (N_TB) phase has emerged as a fascinating phenomenon in the field of supramolecular chemistry, based on complex intermolecular interactions. Through a careful analysis of molecular structures and dynamics, we elucidate how these intermolecular interactions drive the complex twist-bend modulation observed in the N_TB. The study employs broadband dielectric spectroscopy spanning frequencies from 10 to 2 × 10⁹ Hz to investigate the molecular orientational dynamics within the glass-forming thioether-linked cyanobiphenyl liquid crystal dimers, namely, CBSC7SCB and CBSC7OCB. The experimental findings align with theoretical expectations, revealing the presence of two distinct relaxation processes contributing to the dielectric permittivity of these dimers. The low-frequency relaxation mode is attributed to an “end-over-end rotation” of the dipolar groups parallel to the director. The high-frequency relaxation mode is associated with precessional motions of the dipolar groups about the director. Various models are employed to describe the temperature-dependent behavior of the relaxation times for both modes. Particularly, the critical-like description via the dynamic scaling model seems to give not only quite good numerical fittings, but also provides a consistent physical picture of the orientational dynamics in accordance with findings from infrared (IR) spectroscopy. Here, as the longitudinal correlations of dipoles intensify, the m₁ mode experiences a sudden upsurge in enthalpy, while the m₂ mode undergoes continuous changes, displaying critical mode coupling behavior. Interestingly, both types of molecular motion exhibit a strong cooperative interplay within the lower temperature range of the N_TB phase, evolving in tandem as the material’s temperature approaches the glass transition point. Consequently, both molecular motions converge to determine the glassy dynamics, characterized by a shared glass transition temperature, T_g. Full article

In recent years, a number of achiral liquid crystal dimer molecules have been shown to exhibit nematic–nematic phase transitions. The lower temperature phase has been identified as the N${}_{\mathrm{TB}}$ phase, which demonstrates emergent chirality in the spontaneous formation of a heliconical structure. Recent fully atomistic simulations of the molecule CB7CB (1,7-bis-4-(4${}^{\prime }$-cyanobiphenyl) heptane), a dimer with an odd number of carbon spacers between the mesogenic parts of the molecule, have captured the N${}_{\mathrm{TB}}$–N–I phase sequence, providing a picture of the order at a molecular level. In this paper, we use atomistic simulations of CB7CB to develop a coarse-grained model using systematic coarse graining in the N${}_{\mathrm{TB}}$ phase. We use both force matching (in the form of the MS-CG method) and iterative Boltzmann inversion (IBI) methodologies. Both techniques capture the heliconical order within the N${}_{\mathrm{TB}}$ phase. Moreover, the model developed via force matching is shown to provide an excellent representation of the atomistic simulation reference model and, remarkably, demonstrates good transferability across temperatures, allowing the N${}_{\mathrm{TB}}$–N and N–I phase transitions to be simulated. We also compare results with those of a Martini 3-based coarse-grained model. Full article

The twist-bend nematic (N_TB) phase of bent-shaped molecules has recently attracted much attention due to the spontaneous bend of its director field and the doubly-degenerate chirality of its heliconical structure. Despite intensive experimental and theoretical investigation worldwide, the main structural characteristics (pitch and conical angle) and elastic properties of the phase are still barely understood. This is mainly due to the difficulty in growing large single domains of the N_TB phase, which prevents the application of the powerful electro-optical techniques developed for the nematic (N) phase. Moreover, the twist and bend distortions of the optic axis are forbidden by the pseudo-layered structure of the N_TB phase, which makes its response to the field smectic-like instead of nematic-like. Therefore, the only macroscopic electric effect that can be observed deep in the N_TB phase is the smectic-like “electroclinic” effect (ECE_NTB). Here, we achieve large monochiral N_TB domains which remain uniform over a wide temperature range (20–60 °C) in thin (1.5 µm) planar cells, thus avoiding the so-called stripe- and rope-like textural instabilities. This allowed us to experimentally determine, using electro-optical measurements, the temperature dependence of the ECE_NTB response in four different N_TB materials: namely the dimers CB7CB, CB9CB, CB6OCB, and BNA76. For all compounds, the thermal dependences of conical angle and pitch in the vicinity of the N-N_TB transition follow the theoretically predicted power law behaviour. However, the agreement between the measured and predicted power law exponents remains only qualitative, which calls for improvement of the theoretical models. Full article