Structural Understanding, Photoswitchability, and Supergelation of a New Class of Four Ring-Based Bent-Shaped Liquid Crystal.

Herein, we report a new type of azobenzene-based unsymmetrical bent-core molecules exhibiting photoswitchability in the liquid crystalline state, solid state, and solution state and in mixture upon UV irradiation and intense visible light. The compounds exhibited solid-state photochromism upon exposure to UV light, whereas in liquid crystalline state, reversible phase transitions were observed via both UV irradiation and intense visible light exposure. Crystal structure analysis reveals the basic structural understanding such as nonplanar bent molecular shape, antiparallel arrangement of the polar bent molecules, intra- and intermolecular hydrogen bonding, and different π-π interactions and interdigitation of long alkyl chains. The compounds are also found to act as supergelator toward various organic solvents. Hence, this is an excellent example of such potential bent-shaped liquid crystals that promise an immense perspective for device applications such as optical storage, molecular switches, etc.

Nanodoping: a route for enhancing electro-optic performance of bent core nematic system.

We report the effect of dispersion of barium titanate (BaTiO3) nanoparticles (BNPs) in a four ring bent core nematic (BCN) liquid crystal. Polarizing optical microscopy reveals the presence of a single nematic phase in pure and doped states. Polar switching has been observed in the bent core system and the value of spontaneous polarization (P s) increases with increase in doping concentration of BNPs in BCN. Dielectric study shows a lower frequency mode, which can be ascribed to the formation of cybotactic clusters. These clusters are also responsible for the observed polar switching in pure, as well as, in doped BCNs. Another higher frequency mode, observed only in pure BCN, indicates the rotation of molecules about their long molecular axis. The conductivity of doped samples is also found to decrease as compared to the pure BCN. This reduction helps in the minimization of negative effects caused by free ions in liquid crystal based devices. This study demonstrates that the interaction between BNPs and BCN molecules improves the P s, dielectric behaviour, viscosity and reduces the conductivity of pure BCN. Hence, nanodoping in a BCN is an effective method for the enhancement of electro-optic performances and will lead to the development of faster electro-optic devices.

Synthesis and Liquid Crystalline Properties of Unsymmetrically Substituted Naphthalenediimides with a Polar Headgroup: Effect of Amide Hydrogen Bonding and Alkyl Chain Length.

A series of new unsymmetrically substituted naphthalenediimide (NDI) moieties NDI-1 to NDI-6 were synthesized. The structures of these compounds were confirmed by means of FT-IR, 1H NMR, 13C NMR, ESI-mass and HRMS spectroscopic measurements. UV/Vis and fluorescence spectroscopy were employed to investigate the photophysical properties of the prepared compounds in solution and in the solid state. Using the onset of UV/Vis absorption, the optical band gaps were calculated. Cyclic voltammetry measurements were performed to study the electrochemical behavior and to calculate the LUMO energy levels. The thermal properties of NDI derivatives were studied by differential scanning calorimetry. The mesomorphic birefringent behavior of the NDI derivatives was investigated with polarizing optical microscopy. Among all of the studied NDI derivatives, only NDI-1, NDI-2, and NDI-3 showed liquid crystalline texture, owing to the presence of an amide linkage for H-bonding along with aromatic moieties for π-π-stacking.

Elastic and dielectric properties of ferroelectric nanoparticles/bent-core nematic liquid crystal blend.

Bent-core liquid crystals present the first evidence of forming polar superstructures from achiral molecules. The nematic phase is the newest member of the bent-core family and turns out to be extremely interesting owing to its distinct features compared to its calamitic counterpart. Here the investigation of one achiral unsymmetrical 2-methyl-3-amino-benzoic acid (2,6-substituted toluene)-derived four-ring bent-core nematic (BCN) liquid crystals (11-2M-F) is presented after nanodispersion. Ferroelectric nanoparticles significantly affect the phase transition temperature, threshold voltage, dielectric permittivity, elastic constants and splay viscosity of the pristine BCN. In most bent-core nematic liquid crystals the bent elastic constant (K33) is usually lower than the splay elastic constant (K11) owing to the presence of short-range smectic-C-like correlations in the nematic phase. Thus the elastic anisotropy ([Formula: see text]) is usually negative in bent-core nematics unlike in rod-like nematic liquid crystals where K33 is always greater than K11. Here we report a short-core bent-shaped nematic liquid crystal whose negative elastic anisotropy was turned to positive by minute addition of ferroelectric nanoparticles.

Highly Polarized Fluorescent Illumination Using Liquid Crystal Phase.

Liquid crystal (LC) materials are currently the dominant electronic materials in display technology because of the ease of control of molecular orientation using an electric field. However, this technology requires the fabrication of two polarizers to create operational displays, reducing light transmission efficiency below 10%. It is therefore desirable to develop new technologies to enhance the light efficiency while maintaining or improving other properties such as the modulation speed of the molecular orientation. Here we report a uniaxial-oriented B7 smectic liquid crystalline film, using fluorescent bent-core LC molecules, a chemically modified substrate, and an in-plane electric field. A LC droplet under homeotropic boundary conditions of air/LC as well as LC/substrate exhibits large focal conic like optical textures. The in-plane electric field induced uniaxial orientation of the LC molecules, in which molecular polar directors are aligned in the direction of the electric field. This highly oriented LC film exhibits linearly polarized luminescence and microsecond time-scale modulation characteristics. The resultant device is both cheap and easy to fabricate and thus has great potential for electro-optic applications, including LC displays, bioimaging systems, and optical communications.

Fluorescence confocal polarizing microscopy of a fluorescent bent-core liquid crystal exhibiting polarization splay modulated (B7) structures and defects.

The B7 phases of bent-core molecules are polarization splay modulated fluid smectics that exhibit an unusually complex variety of exotic macroscopic structures, textures, and defects visible in polarized light microscopy. Herein we describe optical studies of these structures using fluorescence confocal polarizing microscopy (FCPM) and depolarized transmission optical microscopy to probe their organization in three dimensions. These experiments utilize recently reported fluorescent bent-core molecules designed to give strong polarized fluorescence. This new bent-core molecular family provides the means for probing a variety of bent-core phases and structures by using FCPM and multiphoton fluorescence nonlinear imaging techniques. Comparative textural analysis of the B7 structures obtained using different types of imaging and the corresponding structural models are discussed.

Homeotropic alignment and director structures in thin films of triphenylamine-based discotic liquid crystals controlled by supporting nanostructured substrates and surface confinement.

We explore the effects of nanoscale morphology of supporting solid substrates on alignment, defects, and director structures exhibited by thin films of triphenylamine-based discotic liquid crystals. Fluorescence confocal polarizing microscopy and intrinsic polarized fluorescence properties of studied molecules are used to visualize three-dimensional director fields in the liquid crystal films. We demonstrate that, by controlling surface anchoring on supporting or confining solid substrates such as those of carbon nanotube electrodes on glass plates, both uniform homeotropic and in-plane (edge-on) alignment and nonuniform structures with developable domains can be achieved for the same discotic liquid crystal material.

Organization of the polarization splay modulated smectic liquid crystal phase by topographic confinement.

Recently, the topographic patterning of surfaces by lithography and nanoimprinting has emerged as a new and powerful tool for producing single structural domains of liquid crystals and other soft materials. Here the use of surface topography is extended to the organization of liquid crystals of bent-core molecules, soft materials that, on the one hand, exhibit a rich, exciting, and intensely studied array of novel phases, but that, on the other hand, have proved very difficult to align. Among the most notorious in this regard are the polarization splay modulated (B7) phases, in which the symmetry-required preference for ferroelectric polarization to be locally bouquet-like or "splayed" is expressed. Filling space with splay of a single sign requires defects and in the B7 splay is accommodated in the form of periodic splay stripes spaced by defects and coupled to smectic layer undulations. Upon cooling from the isotropic phase this structure grows via a first order transition in the form of an exotic array of twisted filaments and focal conic defects that are influenced very little by classic alignment methods. By contrast, growth under conditions of confinement in rectangular topographic channels is found to produce completely new growth morphology, generating highly ordered periodic layering patterns. The resulting macroscopic order will be of great use in further exploration of the physical properties of bent-core phases and offers a route for application of difficult-to-align soft materials as are encountered in organic electronic and optical applications.

Photoinduced circular anisotropy in a photochromic W-shaped-molecule-doped polymeric liquid crystal film.

Photoinduced circular anisotropy has been demonstrated in thin films of a main-chain polymeric liquid crystal (PLC) system doped with photochromic W-shaped molecules containing two azobenzene groups by irradiating with circularly polarized light (CPL). Reversible photoinduced circular dichroism (CD) was observed with sign relevant to the handedness of the CPL. The experimentally observed CD spectra were analyzed using the DeVoe polarizability model associated with the coupled oscillator method. We also propose a mechanism for the photoinduced circular anisotropy in our system; nucleating the W-shaped molecules with preferential twisted conformation by CPL irradiation, and triggering the local formation of a chiral structure in the W-shaped-molecule-doped main-chain PLC medium.