Volume generation towards dynamic surface morphing in liquid crystal polymer networks

ABSTRACT

Thin coatings based on liquid crystal networks (LCNs) modified with azobenzene moieties are able to create dynamic surface topographies in the micrometre range by exposure with UV light. The surface corrugations can be erased and restored by switching ‘off’ and ‘on’ the UV illumination. Various configurations were presented. The formation of the protrusions was proven to be induced mainly by excessive volume formation when the order in the LCNs is reduced. It is suggested that this extra volume formation can be further enhanced by stimulating the oscillatory dynamics of trans-cis and cis-trans isomerisation. Therefore, dual-wavelength exposure not only exciting the trans state of azobenzene by 365 nm UV light but simultaneously also the cis state by 455 nm blue light was shown to enhance the effect.     

Photo-responsive polysiloxane-based azobenzene liquid crystalline polymers prepared by thiol-ene click chemistry

In this work, a novel polysiloxane-based azobenzene-containing liquid crystalline polymer (LCP) PMMS-A44V6 has been designed and synthesized via a facile thiol-ene click chemistry method by grafting a side-on azobenzene mesogenic group A44V6 onto poly-[3-mercaptopropylmethylsiloxane] (PMMS) backbone. ¹H NMR, ¹³C NMR, GPC, TGA, DSC, POM and WAXS were used to investigate the mesogenic properties and photo-responsive behaviour of PMMS-A44V6. Taking advantage of the azobenzene’s trans–cis isomerization effect, PMMS-A44V6 can perform an isotropization process under UV irradiation in its nematic phase. Initially, the isotropization process starts in a linearly decreasing manner with a rate of ca ?6.5 × 10⁵ intensity/s, and eventually finishes in an exponential decrease regime to form cis-azobenzene moieties. The reversible UV-response behaviour of PMMS-A44V6 can be performed in a relatively low temperature range of 30 ~ 75°C, which might help this azobenzene-containing LCP material to find potential application in control 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.     

Anomalous optical properties of photoactive cholesteric liquid crystal doped with single-walled carbon nanotubes

Optical transmission and selective reflection data are reported for suspensions of single-walled carbon nanotubes (CNTs) in photoactive nematic material ZhK-440 with a mesogenic chiral dopant M5. At small concentrations of CNTs (C ≈ 0.01–0.05%), the preferential localisation of CNTs at oily sticks (cholesteric topological defects) and suppression of the network of oily streaks by CNTs were observed. At the same time, the optical density D was shown to be essentially non-linear and a minimum at certain concentration of CNTs, C ≈ 0.05–0.08%, was observed. This anomalous behaviour was explained by the presence of the structural transition from the loose (ramified) aggregates with highly anisotropic shape (oriented along the anchoring direction on rubbed polyvinyl alcohol) to the compact aggregates with denser packing. The location of this minimum, as well as the selective reflection maximum (helical pitch), was sensitive to partially reversible UV-induced trans–cis–trans isomerisation effects. The UV-controlled helical pitch variation was shown to be only slightly affected by introduction of CNTs.     

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.     

Liquid crystalline non-linear S-shaped oligomers consisting of azobenzene and biphenylene units: synthesis,characterisation and influence of central spacer

A series of non-linear S-shaped liquid crystal oligomers wherein the molecule consists of biphenylene moiety as a central core unit and two symmetrical side arms azobenzene moieties joined to catechol as a linkage group have been successfully synthesised and characterised. The members in this series possess different inner spacer with carbon number n ranging from 4 to 9 while the outer spacer length located in azobenzene moieties are remains unaltered. The members with even parity exhibit monotropic phase, whereas homologues with odd parity display enantiotropic phase. The appearance of nematic, smectic A and smectic B phases was validated with texture observation under polarised light and X-ray diffraction (XRD). The XRD study on the S-shaped oligomer indicates that the arrangement of smectic phase exists as an intercalated structure. The S-shaped oligomer shows photoisomerisation properties in solution whereby the trans to cis isomerisation for this molecule is accomplished 1140 s, whereas reverse process under thermal back reaction occurred in 4620 min.     

Synthesis and photoswitching properties of bent-shaped liquid crystals containing azobenzene monomers

Three novel bent-shaped monomers, namely 1,3-phenylene bis-{4-[4-(n-allyloxyalkyloxy)phenylazo]benzoate} 5a–c, containing azobenzene as side arms, resorcinol as central units and terminal double bonds as polymerisable functional groups were synthesised and characterised. The mesophase behaviour was investigated by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction measurements and it was found that all three compounds display SmA_intercal mesophases. These bent-shaped molecules exhibit strong photoisomerisation behaviour in solutions in which trans to cis isomerisation takes about 50 seconds whereas the reverse process takes almost 31 hours.     

Liquid crystal dimers containing Cholesteryl and Triazole-containing mesogenic units

ABSTRACT

New liquid crystals categorised as cholesteryl dimers have been successfully synthesised through the reaction between cholesteryl 4-(prop-2-ynyloxy)benzoate moieties with n-azido(cholesteryloxy-carbonyl)alkane. All the dimers display enantiotropic mesophases. Whilst the odd-numbered dimers exhibit chiral nematic (N*), twisted grain boundary (TGB) and chiral smectic C (SmC*) phases, the even-numbered members from the same series show chiral smectic A and C. A detailed inspection on mesophase reveals that the chiral centres and the bent conformation of the odd-numbered members are essential for the induction of TGB phase. However, upon decreasing the temperature, the ratio of the transition temperatures (T_SmC*-SmA*/T_SmA*-I) is found to be 0.95, which indicate the second order transition according to the McMillan’s molecular theory. In addition, the X-ray diffraction study supports the presence of the smectic A phase on the even members rather than the N* by the appearance of the Bragg diffraction peaks at 190°C. A comparison study with the other analogues in which the cholesterol entity is substituted by azobenzene or biphenyl tails has been carried out to assess the relationship between the molecular structure and mesomorphic behaviour.     

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.     

Tuning helical twisting power and photoisomerisation kinetics of axially chiral cyclic azobenzene dopants in cholesteric liquid crystals

ABSTRACT

Significant attention has been paid to improve the helical twisting power (β) and Δβ between the two different isomers of axially chiral azobenzene dopants in cholesteric liquid crystals (CLCs); however, the correlations between the vales (β and Δβ) with the molecular structures as well as photoisomerisation kinetics are far from clear. In this study, a series of binaphthyl-azobenzene cyclic dopants R1–R3 with different lengths of alkoxy chain was synthesised, which exhibited photochemically reversible trans–cis isomerisation in both organic solvents and liquid crystal hosts. When doping into a nematic liquid crystal, dopant R2 with one linking alkoxy group showed the highest values of β and Δβ. The results revealed that the β value was related to the dihedral angle between two naphthyl planes and the miscibility between the dopants and the host molecule. Moreover, Δβ was also depended on the photoisomerisation quantum yields. With increasing length of alkoxyl chain, the photoisomerisation rate constant of dopants increased upon ultraviolet irradiation and decreased for the reverse process upon visible light irradiation either in isotropic acetonitrile or in CLCs. These results enable the precise tuning of the pitch and selective reflection wavelength of CLCs.     

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.     

Discontinuous change in the helical pitch of cholesteric liquid crystals by photoisomerization of a chiral azobenzene molecule

This paper describes the discontinuous change in the helical pitch of a cholesteric liquid crystal (ChLC) by means of the photoisomerization of chiral azobenzene molecules under homogenous alignment conditions. A mixture of E44, R811 and Azo was prepared in the ratio 68/28/4, respectively. R811 and Azo have opposite twisting abilities such that they induce right- and left-handed helices, respectively when added to E44. The mixture was injected into a glass cell having a 2 or 5?µm cell gap, and treated for homogeneous molecular orientation. The wavelength of selective reflection from the ChLC was shifted to shorter wavelengths by the trans-cis photoisomerization of Azo. The change in the helical pitch was not only discontinuous, but also dependent on the cell thickness. The discontinuous change in the helical pitch was estimated to be almost the same as the half turn of the helical pitch in each cell gap, and was dependent on the number of helical half pitches in the glass cell. The homogeneous alignment condition affects the photochemical change in the helical structure of the ChLC system.     

Photochromic liquid-crystalline polymers. Main chain and side chain polymers containing azobenzene mesogens

Abstract

Two classes of thermotropic polymers were synthesized containing the trans-azobenzene unit as both a mesogenic and a photochromic group. In the former class (I) the azobenzene unit is incorporated into the main chain of substituted polymalonates, while in the latter class (II) it is appended as a side chain substituent to a polyacrylate backbone. The liquid-crystalline properties of the polymers were studied as a function of the chemical structure. All of the prepared polymers I have smectic phases. Polymers II are nematic and/or smectic, or cholesteric when including a chiral residue R'. Polymers I and II when radiated at 348 nm in chloroform solution undergo trans-to-cis isomerization of the azobenzene moiety. The calculated rate constants are comparable with those of low molar mass model compounds, and indicate that the macromolecular structure does not significantly affect the photoisomerization rate.     

Photoresponsive Stripe Pattern in Achiral Azobenzene Liquid Crystals

A periodic stripe pattern is found in the nematic phase close to the smectic phase of photoresponsive achiral liquid‐crystalline compounds. The origin of the stripe patterns can be ascribed to an extremely large bent elastic constant K₃₃. In addition, we succeeded in controlling the pattern by the following two methods: 1) the stripe disappears by a trans–cis photoisomerization upon UV light irradiation and reappears upon light termination, and 2) the stripe pattern is stabilized over the whole nematic phase, at approximately 10 °C, by polymerization of the compounds.     

Azo Monomers Exhibiting Low Layer Shrinkage at the SmA–SmC Transition and trans–cis Light‐Induced Isomerization

Methacrylic monomers containing a (phenylene)azobenzene unit substituted with a lateral cyano group and alkyl chains of different length are synthesized and characterized by NMR techniques. Their liquid‐crystalline properties are studied by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction. All monomers exhibit a mesomorphic behavior that extends over wide temperature ranges with nematic and orthogonal or tilted smectic‐type mesophases, depending on the length of the terminal chain. The smectic structures are determined to be single‐layered with a low layer shrinkage (<5 %) at the SmA–SmC transition. This atypical behavior is attributed to the combination of a high smectic order promoted by both π–π and bond dipole–bond dipole interactions between cyano‐substituted central cores, and a low correlation between neighboring layers arising from dispersive forces between the end groups (methacrylic group and alkyl chain) of the monomer. On the other hand, the trans–cis isomerization of monomers is induced in solution by irradiating with a UV lamp. High cis‐isomer contents (≥96 %) are obtained at the photostationary state, which is reached in a relatively short time (40 s).     

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.     

Mechanical Motion of Chiral Azobenzene Crystals with Twisting upon Photoirradiation

The photomechanical motion of chiral crystals of trans‐azobenzene derivatives with an (S)‐ and (R)‐phenylethylamide group was investigated and compared with a racemic crystal. Changes in the UV/Vis absorption spectra of the powdered crystals before and after UV irradiation were measured by using an optical waveguide spectrometer, showing that the lifetime of the cis‐to‐trans thermal back‐isomerization of the chiral crystals was faster than that of the racemic crystals. Upon UV irradiation, a long plate‐like chiral microcrystal bent away from the light source with a twisting motion. A square‐like chiral microcrystal curled toward the light with some twisting. Reversible bending of a rod‐like chiral microcrystal was repeatable over twenty‐five cycles. In contrast, bending of a plate‐like racemic microcrystal was small. A possible mechanism for the bending and twisting motion was discussed based on the optimized cis conformer determined by using calculations, showing that the bending motion with twisting is caused by elongation along the b axis and shrinkage along the a axis.     

Charge-transfer interaction in liquid-crystalline materials and their application to photonics

Photochemical phase transition of push-pull type azobenzene liquid crystal (LC), which contains both an electron donor and an acceptor in both ends of the azobenzene moiety, has been explored. Polymer azobenzene LCs were prepared, which show nematic (N) LC behavior in the trans form while no LC phase in the cis isomer. Photoirradiation of a very thin film of the azobenzene LCs (∼ 200 nm) in the trans form resulted in disappearance of the N phase due to transcis photoisomerization of each mesogen, and the N phase recovered quickly when the irradiated sample was kept in the dark because of cis-trans thermal isomerization and reorientation of trans-azobenzenes. Time-resolved measurements by the use of a laser pulse (355 nm; 10 ns FWHM) revealed that the N to isotropic (I) phase transition took place in 200 μs. The thermal I-N phase transition of the push-pull type azobenzene LC occurred in 800 ms at 135 °C. This response is faster by one order of magnitude than the response of azobenzene LCs without charge-transfer interaction.     

Azobenzene-containing bent-core liquid crystals: an overview

ABSTRACT

Azo-functionalised materials are of special interest due to their photochromic nature, i.e. reversible trans–cis isomerisation upon photoirradiation. The combination of photosensitivity and liquid crystalline properties in the same molecule allows the material to be exploited for optical and optoelectronic devices. Azobenzene-based bent-core liquid crystals (BCLCs) have attracted considerable attention in recent years due to their rich mesomorphism. In this review, the main research directions and different molecular structures of bent-core molecules incorporating azobenzene unit and its subtype the so-called hockey-stick molecules are summarised. Additionally, azobenzene-based U-shaped molecules, hydrogen-bonded bent-shaped liquid crystalline materials and some selected examples of two different types of photoswitchable mesogenic dimers are provided. The nature, number and position of the lateral substitutions able to modify the phase behaviour of such BCLCs, affording in turn interesting liquid crystalline phases are discussed. Finally, the isomerisation process of these photosensitive BCLCs in solutions or in mesophases under the effect of UV–visible irradiation is summarised.     

Blue phase liquid crystals affected by graphene oxide modified with aminoazobenzol group

Liquid-crystalline blue phases (BPs) are stable only for very narrow temperature range between the isotropic and the chiral nematic phase that severely hinders their applicability. Herein, the aminoazobenzol group was chemically grafted onto epoxy group of graphene oxide (GO) via addition reaction. Successful grafting of aminoazobenzol group was confirmed using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), UV–vis absorption spectra and thermogravimetric analysis (TGA). The resultant aminoazobenzol group–modified GO sheets, which is reduced (RGO-Az), were easily redispersable in common organic solvents or liquid crystals (LCs). By doping different contents of RGO-Az, nanosheets could stabilise BP and increase the BP range. When doped with 0.5 wt% RGO-Az, the mixtures show the wider range with 5.9°C than the range with 3.6°C of BPLCs without RGO-Az. Meanwhile, the phase sequence and the range of the aforementioned phases are reproducible upon heating and cooling, which shows that the BPs doped with RGO-Az nanosheets are thermodynamically stable.