The Shackling Effect in Cyclic Azobenzene Liquid Crystal

We demonstrate here a novel method for the design of liquid crystals (LCs) via the cyclization of mesogens by flexible chains. For two azobenzene-4,4′-dicarboxylate derivatives, the cyclic dimer, cyclic bis(tetraethylene glycol azobenzene-4,4′-dicarboxylate) (CBTAD), shows LC properties with smectic A phase, while its linear counterpart, bis(2-(2′-hydroxyethyloxy)ethyl azobenzene-4,4′-dicarboxylate (BHAD), has no LC phase. The difference is ascribed to the shackling effect from the cyclic topology, which leads to the much smaller entropy change during phase transitions and increases the isotropic temperature greatly for cyclics. In addition, the trans-to-cis isomerization of azobenzene groups under UV-light is also limited in CBTAD. With the reversible isomerization of azobenzene groups, CBTAD showed interesting isothermal phase transition behaviors, where the LC phase disappeared upon photoirradiation of 365 nm UV-light, and recovered when the UV-light was off. Combined with the smectic LC nature, a novel UV-light tuned visible light regulator was designed, by simply placing CBTAD in two glass plates. The scattered phase of smectic LC was utilized as the “OFF” state for light passage, while the UV-light induced isotropic phase was utilized as the “ON” state. The shackling effect outlined here should be applicable for the design of cyclic LC oligomers/polymers with special properties.

     

Photoinduced liquid crystal blue phase by bent-shaped cis isomer of the azobenzene doped in chiral nematic liquid crystal

A photoresponsive azobenzene molecule DCAZO2 with two cholesteryl groups linked to both sides of the azobenzene group is doped in a mixture of nematic liquid crystal E7 and chiral dopant S811 (61.9 wt% E7, 36.1 wt% S811 and 2.0 wt% DCAZO2). Cooled from isotropic phase to 33.0°C, chiral nematic liquid crystal (N*LC) was formed in the sample and then the temperature was kept unchanged at 33.0°C. UV light irradiation induces the trans–cis photoisomerisation and thus an obvious phase transition. When the azobenzene groups isomerise to a cis-saturated state, the UV light was turned off and the white light was turned on at the same time. The bent-shaped cis isomer then turns back to the planar trans isomer gradually. A blue–green platelet texture representing cubic blue phase (BP) was observed and the size of the platelets was increased along with the cis–trans isomerisation. UV–vis absorption spectra indicate that the photoinduced BP exists when the isomerisation degree is between 79% and 18%, and further cis–trans isomerisation change BP back into N*LC. The large geometric structure of the cholesteryl groups and the large bent angle θ of the cis isomer are supposed to be responsible for the interesting result.     

Tunable backflow in chiral nematic liquid crystals via twist-bend nematogens and surface-localised in-situ polymer protrusions

Dynamic electro-optic response of the liquid crystal (LC) director shows a backflow effect that is manifested as an optical bounce in chiral nematic LCs (N*LC) during field-induced homeotropic-twisted transition. The bend elastic constant (K₃₃) strongly influences the dynamics of backflow at the N*LC in homeotropic-twisted transition. The cyanobiphenyl LC dimers – CB7CB, CB9CB and CB11CB – possess a unique characteristic of inherent bend molecular configuration that lowers K₃₃. With the modulation of the effective K₃₃ in dimer-doped N*LCs, we report the tunability of the optical bounce that decreases with the increase in the length of flexible spacers in LC dimers. The doped LC dimers with short spacer lengths not only generate a strong backflow with an enhanced twist degeneracy of the LC director across the cell, but also prolong the time of disappearance of the optical bounce. Furthermore, we demonstrate the suppression of the optical bounce with surface localised polymer protrusions having 50–100 nm diameters, which allow faster dynamic relaxation process and reduced backflow. We envision a novel design of a tunable microfluidic device for precise flow control of organic or inorganic matter in LC medium that exploits the tunable backflow in LC dimer-doped N*LCs.     

Bromine-terminated azobenzene liquid crystals

A series of liquid crystals (LCs) of bromine-terminated azobenzene were synthesised and characterised. The LCs were composed of an azobenzene core, an alkyl chain and a flexible spacer with a bromine atom at a remote position. Mesomorphic properties were dependent on both the alkyl chain length and the relative position of the bromine atom at the end of the spacer group. The nematic phase was favoured over the smectic A phase for alkyl chains with one and seven carbon atoms. However, the SmA mesophase was dominant for compounds with 10-carbon alkyl chains. The remote bromine atom in the spacer group favoured SmA for homologous with n-decyl chains and the nematic phase for n-heptyl and methyl groups. Molecular modelling showed that the azobenzene LCs tended to adopt the all trans-conformation in the gas phase as the number of carbon atoms increased. For short spacer groups, bent conformations contributed to the level population proportion of conformers. For the non-LC 5a, the gauche conformation became the most stable with a torsional angle of –68.9°. X-ray experiments showed a monolamellar SmA mesophase in an antiparallel arrangement. Absorption maxima at 360 and 440 nm were assigned to π–π* and n–π* transitions, respectively.     

Synthesis and Characterization of Naphthalene‐Based Banana‐Shaped Liquid Crystals for Photoswitching Properties

A series of banana‐shaped monomers containing naphthalene as central units, azobenzene in side arms with terminal alkenes were synthesized and characterized. Polarizing optical microscopy, DSC and X‐ray diffraction measurements reveal that one compound processes a nematic phase while other four compounds exhibit B₆ phase. The absorption spectrum of trans‐azobenzene displays high‐intensity π‐π* transition at 365 and low‐intensity n‐π* transition at 450 nm. These molecules exhibit strong photoisomerisation behaviour in solutions in which trans to cis isomerisation takes 55 seconds whereas reverse process takes about 32 hours. Such a long thermal back relaxation is useful for creation of optical image storage devices.     

Control of the Orientation and Photoinduced Phase Transitions of Macrocyclic Azobenzene

Photoinduced phase transitions caused by photochromic reactions bring about a change in the state of matter at constant temperature. Herein, we report the photoinduced phase transitions of crystals of a photoresponsive macrocyclic compound bearing two azobenzene groups ( 1 ) at room temperature on irradiation with UV (365 nm) and visible (436 nm) light. The trans/trans isomer undergoes photoinduced phase transitions (crystal–isotropic phase–crystal) on UV light irradiation. The photochemically generated crystal exhibited reversible phase transitions between the crystal and the mesophase on UV and visible light irradiation. The molecular order of the randomly oriented crystals could be increased by irradiating with linearly polarized visible light, and the value of the order parameter was determined to be ?0.84. Heating enhances the thermal cis‐to‐trans isomerization and subsequent cooling returned crystals of the trans/trans isomer.     

trans–cis Photoisomerization of Azobenzene‐Conjugated Dithiolato‐Bipyridine Platinum(II) Complexes: Extension of Photoresponse to Longer Wavelengths and Photocontrollable Tristability

Azobenzene derivatives modified with dithiolato‐bipyridine platinum(II) complexes were synthesized, revealing their highly extended photoresponses to the long wavelength region as well as unique photocontrollable tristability. The absorptions of trans‐ 1 and trans‐ 2 with one azobenzene group on the dithiolene and bipyridine ligands, respectively, cover the range from 300 to 700 nm. These absorptions are ascribed, by means of time‐dependent (TD)DFT calculations, to transitions from dithiolene(π) to bipyridine(π*), namely, interligand charge transfer (CT), π–π*, and n–π* transitions of the azobenzene unit, and π–π* transitions of the bipyridine ligand. In addition, only trans‐ 1 shows distinctive electronic bands, assignable to transitions from the dithiolene(π) to azobenzene(π*), defined as intraligand CT. Complex 1 shows photoisomerization behavior opposite to that of azobenzene: trans‐to‐cis and cis‐to‐trans conversions proceed with 405 and 312 nm irradiation, which correspond to excitation with the intraligand CT, and π–π* bands of the azobenzene and bipyridine units, respectively. In contrast, complex 2 shows photoisomerization similar to that of azobenzene: trans‐to‐cis and cis‐to‐trans transformations occur with 365 and 405 nm irradiation, respectively. Irradiation at 578 nm, corresponding to excitation of the interligand CT transitions, results in cis‐to‐trans conversion of both 1 and 2 , which is the longest wavelength ever reported to effect the photoisomerization of the azobenzene group. The absorption and photochromism of 4 , which has azobenzene groups on both the dithiolato and bipyridine ligands, have characteristics quite similar to those of 1 and 2 , which furnishes 4 with photocontrollable tristability in a single molecule using light at 365, 405, and 578 nm. We also clarified that 1 and 2 have high photoisomerization efficiencies, and good thermal stability of the cis forms. Complexes 3 and 5 have almost the identical photoresponse to those of their positional isomers, complexes 2 and 4 .     

Photo-controllable electro-optic response of liquid crystalline cells using photo-isomeric molecules

A photo-controllable liquid crystal (LC) material was evaluated using a nematic LC mixture with azobenzene. This study aimed to determine the mechanisms that result in variations of material parameters specifically caused by the morphological change of guest molecules. The transition from rod-shaped trans isomers to bent-shaped cis isomers weakened the intermolecular ordering interactions and the decreasing order parameter caused variations of material parameters. The shift of dielectric response cannot be solely explained by the weakened intermolecular interactions but is also significantly influenced by the properties of the guest cis isomer itself. The bend elastic constant was more affected than the splay elastic constant, which implies that the shift of the elastic properties is due to the morphological shape of the cis isomer as well as the decreased molecular ordering. Thus, three different mechanisms are involved in the variations of the material properties: (i) weakened intermolecular ordering interactions, (ii) direct contribution of cis isomers, and (iii) molecular morphological interactions of the cis isomer with the host LCs. It was also demonstrated that the optical properties of twisted nematic (TN) cells can be controlled, and that the stability of the bend state in the optically compensated birefringence (OCB) mode cell can be improved.     

Photo-induced control of bubble domains in chiral–nematic liquid crystal by a violet laser beam

The stable bubble domains generated by mixing 10% of chiral molecules into an azobenzene liquid crystal (LC)-doped nematic host can be optically controlled by a violet laser beam (415 nm). The photon-induced reversible trans–cis photo-isomerisation of azobenzene changes the helical twisting power (HTP) of LC mixtures in which the HTP of cis-azobenzene LC is lower than trans-azobenzene LC. Under the irradiation of an optical field (>20 mW cm^???2), the helical pitch distance, which is inverted proportional to the HTP, increases and the bubble domains disappear. Immediate obstruction of laser light irradiation initiates cholesteric nucleation, merging of domains and the subsequent generation of stably dispersed bubble domains.     

Light-Responsive Oligothiophenes Incorporating Photochromic Torsional Switches

We present a quaterthiophene and sexithiophene that can reversibly change their effective π-conjugation length through photoexcitation. The reported compounds make use of light-responsive molecular actuators consisting of an azobenzene attached to a bithiophene unit by both direct and linker-assisted bonding. Upon exposure to 350 nm light, the azobenzene undergoes trans-to-cis isomerization, thus mechanically inducing the oligothiophene to assume a planar conformation (extended π-conjugation). Exposure to 254 nm wavelength promotes azobenzene cis-to-trans isomerization, forcing the thiophenic backbones to twist out of planarity (confined π-conjugation). Twisted conformations are also reached by cis-to-trans thermal relaxation at a rate that increases proportionally with the conjugation length of the oligothiophene moiety. The molecular conformations of quaterthiophene and sexithiophene were characterized by using steady-state UV-vis spectroscopy, X-ray crystallography and quantum-chemical modeling. Finally, we tested the proposed light-responsive oligothiophenes in field-effect transistors to probe the photo-induced tuning of their electronic properties.     

New symmetric azobenzene molecules of varied central cores: Synthesis and characterisation for liquid crystalline properties

A new series of azobenezene liquid crystals (LCs) was designed and synthesised by known and straightforward methods. The central connecting cores of the molecules varied viz., benzene/naphthalene/biphenyl. The molecular structures were confirmed by infrared, UV, nuclear magnetic resonance spectroscopic techniques. The LC texture and thermal phase behaviours were investigated by polarising optical microscopy and differential scanning calorimetry. Smectic B phase was found in biphenyl-derived azobenzene ester. The effect of central core on LC properties was investigated. The decreased angle at central connecting core suppressed the melting points, phase transition temperatures without losing LC properties, whereas, in moderate angle compounds LC properties were suppressed. The compounds with increased angle at central core favours rich mesomorphism.     

Supramolecular Tubule from Seesaw Shaped Amphiphile and Its Hierarchical Evolution into Sheet

Although supramolecular one‐dimensional (1D) and two‐dimensional (2D) structures with various unique properties have been extensively studied, the reversible switching between tubules and sheets via lateral association remains challenging. Here, we report the unique structures of a supramolecular tubular bamboo culm in which the hollow‐tubular interior is separated, at intervals, by nodes per 1.3 nm. Interestingly, the discrete tubules are able to hierarchically assemble into a flat sheet in response to an aromatic guest. The addition of trans‐azobenzene, as a guest, enables the tubules to form a hierarchical sheet assembly via the lateral interaction. The hierarchical sheet structures are disassembled into their constituent tubules upon UV irradiation due to trans‐cis isomerization. The recovery from cis‐azobenzene to trans‐form induces repeatedly the hierarchical sheet assembly, indicative of a reversible switching behavior between tubules and sheets triggered by an external stimulus.     

Doubly photoresponsive and water‐soluble block copolymers: Synthesis and thermosensitivity

We report the synthesis and investigation of a new type of photoresponsive block copolymers (BCPs). They were designed to comprise two water‐soluble polymers containing two different photoisomerizable moieties (either azobenzene and spiropyran or two different azobenzenes), with the two constituting blocks that, when separated, exhibit a lower critical solution temperature (LCST) in water and can shift their LCST in opposite directions upon photoisomerization (decrease of LCST for one polymer and increase for the other). A variety of such doubly photoresponsive BCPs were synthesized using either azobenzene‐ or spiropyran‐containing poly(N,N‐dimethylacrylamide) (PDMA), poly(N‐isopropylacrylamide) (PNIPAM) and poly[methoxydi(ethylene glycol) methacrylate] (PDEGMMA). Their thermal phase transition behaviors in aqueous solution before and after simultaneous photoreactions on the two blocks were investigated in comparison with their constituting blocks, by means of solution transmittance (turbidity) and variable‐temperature ¹H NMR measurements. The results show that BCPs displayed a single LCST whose shift upon two photoisomerizations appeared to be determined by the competing and opposing photoinduced effects on the two blocks. Moreover, optically controlling the relative photoisomerization degrees of trans azobenzene‐to‐cis azobenzene and spiropyran‐to‐merocyanine could be used to tune the LCST of BCP solution. This study demonstrates the potential of exploring a more complex photoreaction scheme to optically control the solution properties of water‐soluble thermosensitive BCPs. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4055–4066, 2010     

Temperature dependent light transmission-light scattering switching of (homeotropic liquid crystalline polymer network/liquid crystals/chiral dopant) composite film

A (photo-polymerizable liquid crystal (LC) monomer/LCs/chiral dopant/photoinitiator) mixture with a smectic A (SmA)-chiral nematic (N*) phase transition was sandwiched between two ITO glass substrates which were not subjected to any surface orientation treatment. When an electric field-induced homeotropically oriented SmA phase of the mixture was irradiated with UV light, an oriented liquid crystalline polymer (LCP) network was formed upon photo-polymerization of the LC monomer. Then, a (homeotropically oriented LCP network/LCs/chiral dopant) composite with a SmA-N* phase transition was prepared. A focal-conic texture appeared in the heat-induced N* phase of the composite upon heating from the transparent state of the homeotropically oriented SmA phase; the focal-conic texture exhibited strong light scattering. Upon cooling the composite to the SmA phase, this phase was again homeotropically oriented due to the strong intermolecular interaction between the LC molecules and the homeotropically oriented LCP network. Thus, the transparent state of the SmA phase and the light scattering state of the N* phase occurred reversibly upon cooling and heating, accompanied by the thermal SmA-N* phase transition.     

Temperature dependent light transmission-light scattering switching of (homeotropic liquid crystalline polymer network/liquid crystals/chiral dopant) composite film

A (photo-polymerizable liquid crystal (LC) monomer/LCs/chiral dopant/photoinitiator) mixture with a smectic A (SmA)-chiral nematic (N*) phase transition was sandwiched between two ITO glass substrates which were not subjected to any surface orientation treatment. When an electric field-induced homeotropically oriented SmA phase of the mixture was irradiated with UV light, an oriented liquid crystalline polymer (LCP) network was formed upon photo-polymerization of the LC monomer. Then, a (homeotropically oriented LCP network/LCs/chiral dopant) composite with a SmA-N* phase transition was prepared. A focal-conic texture appeared in the heat-induced N* phase of the composite upon heating from the transparent state of the homeotropically oriented SmA phase; the focal-conic texture exhibited strong light scattering. Upon cooling the composite to the SmA phase, this phase was again homeotropically oriented due to the strong intermolecular interaction between the LC molecules and the homeotropically oriented LCP network. Thus, the transparent state of the SmA phase and the light scattering state of the N* phase occurred reversibly upon cooling and heating, accompanied by the thermal SmA-N* phase transition.     

Polymorphic transitions mediated by surfactants in liquid crystal nanodroplet

Recently, various techniques have been developed using photonic crystals. Liquid crystals (LC) confined in a nanodroplet mimicked photonic crystals, such as those of opal. Therefore, investigating the phase behaviour of LC molecules in nanodroplets is very important in the next-generation optical field. In this study, the chemical interaction between surfactants and LCs in nanodroplets is reproduced using a dissipative particle dynamics method. We identify the phase behaviour of LCs and investigate how the chemical interaction affect on the orientation of LCs. In particular, by adding surfactant molecules, various morphological behaviours were observed in the LC nanodroplet. The phase transition temperature varied depending on R_ND (amount of surfactant molecules). Furthermore, difference of the self-assembly structure also appeared inside the droplet depending on R_ND. Our simulation offers a theoretical guide to control morphologies of self-assembled LCs inside a nanodroplet, a novel system that may find applications in nanofluidic devices or in photonic crystal technology.     

Photoaddressable polymers for liquid crystal alignment

We demonstrate reversible photoinduced in situ reorientation of low molecular mass liquid crystals (LCs) by means of photoaddressable polymers (PAPs). These polymers contain mesogenic azobenzene side chains optimized to reorient cooperatively and effectively upon illumination with polarized light. Various low molecular mass LCs were introduced between two PAP layers and these sandwich devices were tested with respect to stability and reversibility of photoinduced orientation. Dissolution of the PAP layer by the low molecular mass LC was observed for several material combinations and systematically investigated. Different anisotropic dyes were added as fluorescence markers in order to monitor the photoinduced LC orientation. With an optimized material combination, more than 10 reversible reorientation processes could be realized with polarized light of either 514 or 405 nm wavelength, without any reduction in alignment quality. Further, microscopic polarized fluorescence patterns could be produced and erased within short exposure times.     

Dielectric properties of two high birefringence liquid crystal mixtures in the Sub-THz band

ABSTRACT

In order to produce liquid crystal (LC) with high birefringence (Δn) in the THz band, eight LC monomers were designed and synthesized. We formulate two mixtures (LC S200-2 and E7-2) by adding eight LC monomers to two commercial LCs (S200 and E7), respectively. The dielectric constants of the mixture LCs were measured using the frequency selective surface (FSS) in the region from 90 to 140 GHz. We compare the simulated results with the experimental measurements and determine the dielectric constants of the LCs. The dielectric anisotropy (Δε) of the nematic S200-2 and E7-2 LC mixtures are 16.4% and 16.3% higher than that of the commercial S200 and E7 LCs, respectively. The results show the frequency tunability of the two LC mixtures is greater than that of the commercial LCs.     

Unique Supramolecular Liquid‐Crystal Phases with Different Two‐Dimensional Crystal Layers

We report herein a series of tetrablock‐mimic azobenzene‐containing [60]fullerene dyads that form supramolecular liquid crystals (LCs) from phase‐segregated two‐dimensional (2D) crystals. The unique double‐, triple‐, and quadruple‐layer packing structure of fullerenes in the 2D crystals leads to different smectic supramolecular LC phases, and novel LC phase transitions were observed upon changes in the fullerene packing layer number in the 2D crystals. Interestingly, by combining the LC properties with 2D crystals, these materials show excellent electron mobility in the order of 10⁻³ cm² V⁻¹ s⁻¹, despite their relatively low fullerene content. Our results provide a novel method to manipulate 2D crystal layer thickness, with promising applications in optoelectronic devices.     

Photoinduced switching in self-assembled multilayers of azobenzene-containing ionene polycations and anionic polyelectrolytes

Ultrathin molecular assemblies of new ionene polysoaps bearing azobenzene units in the main chain and anionic polyelectrolytes have been prepared upon electrostatic layer-by-layer adsorption on charged substrates. Ionenes could be adsorbed in the trans- and cis-rich state of their azobenzene units. Use of cis-rich polymer was found to be advantageous because up to three times more material could be adsorbed per dipping cycle as from the solution of the trans polymer. Alternate irradiation with UV (<370 nm) and visible (>450 nm) light allowed to switch between the trans isomer and the cis-rich photostationary state. Photoconversion of ionenes in multilayers is lower than in solution, but higher than for multilayers of azobenzene bolaamphiphiles reported recently.