Azobenzene Mesogens Research Articles

Photo-triggered assembly/disassembly of macroscopically ordered monodomain lamellar structure in side-chain liquid crystalline polymer containing strong polar azobenzene mesogens

Assembly of ordered structures by an external stimulus allows for design of functional materials with enhanced physical and chemical properties. A new side-chain liquid crystal polymer containing strong polar azobenzene mesogens was synthesised. A macroscopically ordered monodomain smectic-like lamellar structure having orientational order and positional order was immediately assembled by linear polarised light irradiation (473 nm, 20 mW/cm2) at room temperature. The lamellar layer with its periodic d-spacing of 1.9 nm and mesogens arranged at an inclination angle of about 75° were characterised by X-ray diffraction and polarising optical microscopy which showed a diffraction peak at 2θ = 4.53° and an off-centred interference figure. Reversible assembly and disassembly of the lamellar phase were achieved by alternative irradiation with polarised light and non-polarised light. Potential factors influencing the assembly of the ordered lamellar structure were investigated by controlling the mesogens out-of-plane orientation and by changing the polarities of mesogens. The difference in arrangement of the mesogens between the lamellar phase and a thermotropic smectic phase was also compared by heating the selectively exposed film. The light controllable assembly of mesogens provides an easy route to assemble a lamellar phase in azobenzene containing polymers for application in optical and photonic devices.

Microphase-separated block copolymer film anchored on ITO substrate with newly designed self-assembled monolayer

ABSTRACTThe surface of Indium-tin-oxide (ITO) substrate was modified with a newly designed silane coupling molecule bearing azobenzene moiety. The silane coupling molecules formed self-assembled monolayer (SAM) on pretreated ITO surface. The SAM growth and coverage were quantified by contact angle measurement and X-ray photoelectron spectroscopy (XPS). The silane coupling molecules improved the adhesion between the ITO surface and an amphiphilic block copolymer (BC) thin film, which consists of poly(ethylene oxide) (PEO) and poly(methacrylate) (PMA) with azobenzene mesogens, because the azobenzene moieties of the SAM anchor the liquid crystalline PMA azobenzene domains of BC.

Light-responsive block copolymer vesicles based on a photo-softening effect

We report the synthesis and study of two series of amphiphilic block copolymers (BCPs) of which the hydrophilic block is either poly(acrylic acid) (PAA) or poly(N,N-dimethylacrylamide) (PDMA) and the hydrophobic block is a side-chain liquid crystalline polymer (SCLCP) bearing biphenyl mesogens in majority and azobenzene mesogens in minority, namely, a random copolymer of 6-[4-(4-cyanophenyl)phenoxyl]hexyl acrylate with 6-[4-(4-methoxyphenylazo)phenoxyl]hexyl acrylate (P(BiPA-co-Azo)). Samples of both BCPs, PDMA-b-P(BiPA-co-Azo) and PAA-b-P(BiPA-co-Azo), could form large vesicles in aqueous solution with a SCLCP membrane. The BCPs were designed for investigating photoinduced order-disorder transition of the mesogens confined inside the vesicle membrane as a result of the trans–cisphotoisomerization of azobenzene and the LC cooperative effect. From photo-optical measurements on a BCP vesicle solution, we found evidence that a photoinduced LC order–disorder transition could occur inside the vesicle membrane in aqueous solution. Moreover, using a pH-sensitive fluorescent probe, we studied the photo-softening effect on the proton transfer across the vesicle membrane. Similar to plasticization of the vesicle membrane upon addition of a good solvent in aqueous solution, photo-induced softening could increase the rate of proton diffusion from inside to outside of the vesicle through the SCLCP membrane.

Nanostructure Dependent Surface Energy of Silica Nanorod Arrays through Block Copolymer Templating Processes

ABSTRACTThe self-assembled block copolymer films with poly (ethylene oxide) (PEO) and hydrophobic polymetharylate (PMA) with azobenzene mesogen in the side chain, denoted as PEOm-b-PMA(Az)n, were used as the template to prepare hexagonally ordered silica nanorod arrays by immersing the template films in the silicate precursor containing tetraetoxysilane (TEOS). The diameter and the center-to-center distance of the SiO2 nanorod arrays were controlled by selecting the block copolymer with different PEO volume fraction. In addition, the contact angles of different kinds’ solvents for the SiO2 nanorod arrays were characterized. We further found, the diameter and the period distance of silica nanorods are very important factors for controlling the contact angle of different kind’s solvents on the surface of the SiO2 nanorod arrays.

Intriguing liquid crystalline behavior of liquid crystalline polyrotaxane containing azobenzene mesogens

A series of liquid crystalline polyrotaxanes containing azobenzene mesogenic moieties (AzoPR) with different length of spacer were synthesized, and the relationship between the spacer length and the liquid crystalline behavior was investigated. The molecular characterization of the AzoPR was performed with 1H NMR, FT-IR, and gel permeation chromatography. The thermal stability was investigated via thermogravimetric analysis. Their phase structures and liquid crystalline properties were studied by differential scanning calorimetry, polarized optical microscopy and wide-angle X-ray diffraction. The experimental results suggested that AzoPR with spacer length of 2 and 4 failed to show the liquid crystalline behavior, and AzoPR with spacer length of 6 showed the columnar nematic phase. However, when the spacer length increases to 11, the columnar nematic phase formed, meanwhile, the liquid crystalline domains with high ordered structure were developed by azobenzene mesogens.

Assemblies of Fluorine Containing Bent-Shaped Liquid Crystal Molecules Studied by Using Scanning Tunneling Microscopy

In this work we prepared a fluorine containing bent-shaped liquid crystal from biphenyl as the central core and rod-like azobenzene mesogens as the side arms, namely 4',3-biphenyl bis[4-(4'-hexadecanloxy-3-fluorophenylazo)benzoate] (L104). The self-assembly behaviors of L104 molecules on graphite surface were investigated by using scanning tunneling microscopy (STM) under ambient conditions. The high-resolution STM images of L104 assemblies revealed three kinds of structures showing the joint effects of dipole-dipole interactions originated from the fluorine and the bent-core alignments for maximizing pi-pi interactions. These observations may be beneficial for understanding the assembly mechanism and designs for novel banana-shaped liquid crystal molecules.

Block Copolymers Comprising π‐Conjugated and Liquid Crystalline Subunits: Induction of Macroscopic Nanodomain Orientation

Block party: A block copolymer comprises both regioregular poly(3-hexylthiophene) (P3HT) and a side-chain liquid-crystalline polymer (SCLCP) bearing azobenzene mesogens. The SCLCP block has a clearing temperature above the high crystal-melting temperature of P3HT, therefore surface- and photoinduced orientation of mesogens in the SCLCP block can be used to align stripelike P3HT nanodomains on the macroscopic scale (see picture for AFM images).

Composite Holographic Gratings Containing Light‐Responsive Liquid Crystals for Visible Bichromatic Switching

Polymeric microstructures, produced in a multi-step chemico-physical process, confine and stabilize a well-aligned nematic liquid crystal (NLC) film, which is doped with a high-performance mesogenic azobenzene dye, sensitive in the visible range.

Cyclic Azobenzene-Containing Side-Chain Liquid Crystalline Polymers: Synthesis and Topological Effect on Mesophase Transition, Order, and Photoinduced Birefringence

A cyclic side-chain liquid crystalline polymer (SCLCP) bearing azobenzene mesogens, namely, poly{6-[4-(4-methoxyphenylazo)phenoxy]hexyl methacrylate} (PAzoMA), was successfully synthesized by using “click” cyclization of the linear polymer precursor with alkyne and azide end groups. Samples of cyclic-PAzoMA of various molecular weights were prepared, characterized, and studied in comparison with their linear counterparts. The results show that the topological constraint arising from the tortuosity of the ring structure and the absence of chain ends in cyclic-SCLCPs affects profoundly the liquid crystalline (LC) phase transitions (temperature, enthalpy, and entropy) of mesogenic side groups and that this topological effect is more prominent for smaller SCLCP rings. Moreover, the photoinduced anisotropy in films as a result of the trans−cis photoisomerization of azobenzene mesogens was investigated, and cyclic-PAzoMA was found to behave differently from linear-PAzoMA. On the one hand, the cyclic polymer exh...

Photoinduced Microphase Separation in Block Copolymers: Exploring Shape Incompatibility of Mesogenic Side Groups

Photoinduced microphase separation in block copolymers (BCP) was achieved for the first time, using a rationally designed diblock copolymer composed of two side-chain liquid crystalline polymers (SCLCP). The miscibility of the two blocks was promoted by the miscibility between the two types of mesognic side groups, while upon UV exposure inducing the trans-cis isomerization of azobenzene mesogens on one SCLCP, the shape incompatibility of bent cis isomers with an ordered liquid crystalline phase drove the separation of the two blocks resulting in a microphase separated morphology. This result shows the perspective of using light to process and organize BCP morphology and related nanostructures in a lithography-free manner.

Tailoring the liquid crystalline property via controlling the generation of dendronized polymers containing azobenzene mesogen

AbstractThe first‐ and second‐generation dendronized polymers containing azobenzene mesogen were designed and successfully synthesized via free radical polymerization. The chemical structures of the monomers were confirmed by elemental analysis, 1H NMR, and 13C NMR. The molecular characterizations of the polymers were performed with 1H NMR and gel permeation chromatography. The phase structures and transition behaviors were studied using differential scanning calorimetry, polarized light microscopy, and small‐angle X‐ray scatter experiments. The experiment results revealed that the first‐generation dendronized polymer exhibited liquid crystalline behavior of the conventional side‐chain liquid crystalline polymer with azobenzene mesogen, that is, the polymer exhibited smectic phase structure at lower temperature and nematic phase structure at higher temperature. However, the second‐generation dendronized polymers exhibited more versatile intriguing liquid crystalline structures, namely smectic phase structure at lower temperature and columnar nematic phase structure at higher temperature, and moreover, the phase structure still remained before the decomposition temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1149–1159, 2010

Design, synthesis, and characterization of a combined main-chain/side-chain liquid-crystalline polymer based on ethyl cellulose

A novel combined main-chain/side-chain liquid-crystalline polymer based on an ethyl cellulose main chain containing azobenzene mesogens (AzoEC) was successfully synthesized. Molecular characterization of the resulting polymers with different degrees of substitution (DS) was performed with proton nuclear magnetic resonance (1H NMR), Fourier-transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). Thermal stability was investigated by thermogravimetric analysis (TGA). The phase transitions and liquid-crystalline behavior of these polymers were investigated by differential-scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). The results indicate that DS has substantial effect on the liquid-crystalline behavior of these polymers. AzoEC with low DS only shows the cholesteric phase similar to ethyl cellulose (EC). However, when DS increases to a specific value, AzoEC begins to show fascinating supramolecular structures. The supramolecular structure of AzoEC with maximum DS consisted of a large-scale ordered lamellar structure formed by EC main chains and a small-scale ordered structure formed by azobenzene mesogens.

Colorimetric response of azobenzene-terminated polydiacetylene vesicles under thermal and photic stimuli

We study the colorimetric reversibility of pure polymerized p-nitro azobenzene moiety-substituted diacetylene (PNADA) and PNADA/polymerized 10,12-pentacosadiynoic acid (PDA) complex vesicles under thermal and photic stimuli. Because of the strong intermolecular interaction among azobenzene mesogens within the vesicles, PNADA vesicles show enhanced stability and completely reversible thermochromic response. Polydiacetylene based complex vesicles with partial reversible chromatic properties under both thermal and photonic stimuli were reported for the first time, which provided a novel model system for the understanding of the chromatic transition mechanism of polydiacetylene materials.

Kinetics oftrans-cisisomerization in azobenzene dimers at an air-water interface

We have studied the kinetics of trans to cis isomerization under the illumination of ultraviolet light, in the Langmuir monolayer of mesogenic azobenzene dimer, bis-[5-( 4' -n-dodecyloxy benzoyloxy)-2-( 4''-methylphenylazo)phenyl] adipate, at an air-water interface. We find that the trans to cis isomerization reaction of the molecules in the monolayer shows deviation from the first-order kinetics unlike those reported on Langmuir monolayers of azobenzene molecules. We attribute the deviation from first-order kinetics to the simultaneous photoisomerization of trans isomers to form cis isomers and the reverse thermal isomerization of cis isomers to form trans isomers. Our analysis of the rate of change of mole fraction of trans isomers to form cis isomers indicates a first-order kinetics for trans to cis photoisomerization reaction and a second-order kinetics for cis to trans thermal isomerization reaction. This second-order kinetics mechanism is similar to the Lindemann-Hinshelwood mechanism for the unimolecular reactions at low concentration of reactants. The formation of the activated cis isomer by collisions is a slow process as compared to the decay of the activated cis isomer to trans isomer in the liquid expanded phase. This results in the second-order kinetics for the thermal isomerization of cis isomers.

Nanohole Arrays Fabricated on Gold Surfaces by Total Wet Nanopatterning through Block Copolymer Masks

Well-ordered nanohole arrays on atomically flat gold (111) surfaces were fabricated by wet etching through block copolymer (BC) masks using ferri/ferrocyanide etchant. Amphiphilic BCs consisting of poly(ethylene oxide) (PEO) and liquid crystalline poly(methacrylate) with azobenzene mesogens [PMA(Az)], PEOm-b-PMA(Az)n, blended with poly(ethylene glycol) monomethylether (EO) form hexagonally arranged ion-transporting nanocylinders of EO-blended PEO microdomains in the BC masks. Atomic force microscopy (AFM) revealed a hexagonally arranged nanohole array on each terrace of the gold surface after the total wet nanopattering including a 5 min etching. The diameter (d) and distance between neighboring nanoholes (D) were controlled by the degree of polymerization of the BC. Two kinds of nanohole arrays with (d, D) = (12 nm, 25 nm) and (20 nm, 41 nm) were obtained in good agreement with the d and D of the EO-blended PEO microdomains of the masks. Scanning tunneling microscopy (STM) indicated that the depth of nanoholes was 3.5 Å, corresponding to the thickness of a single atomic layer of gold, and the flatness of the bottom of the holes was confirmed.

The physical properties of thermotropic side-chain triblock copolymers ofn-butyl acrylate and a comonomer with azobenzene group

The side chain liquid crystal triblock copolymers (TBCs), which underwent phase transitions below their decomposition temperature, were prepared by copolymerization of poly(n-butyl acrylate) and a comonomer containing the mesogenic azobenzene group. The physical properties of TBCs in the distinctive transition temperature ranges were investigated in terms of the liquid crystal (LC) content in the copolymers. The phase transition temperatures traced optically, thermally and rheologically were well coincided one another and clearly exhibited the phase transition of smectic-nematic-isotropic with increasing temperature. In the smectic phase, increasing temperature made the liquid crystal system more elastic, but viscosity (η′) remained almost constant. In the nematic phase, increasing temperature abruptly decreased η′ andG′, ultimately leading to isotropic phase. Both smectic and nematic phases exhibited Bingham viscosity behavior but the former gave much greater yield stress at the same LC content.

Photoresponsive Behavior of Laminated Films Composed of a Flexible Plastic Sheet and a Crosslinked Azobenzene Liquid-Crystalline Polymer Layer with Different Initial Alignment of Mesogens

Laminated films composed of a flexible plastic sheet and a crosslinked azobenzene liquid-crystalline polymer (CLCP) layer with different initial alignment of azobenzene mesogens were prepared by thermal compression bonding of a CLCP film and an unstretched low-density polyethylene (PE) film with an adhesion layer. In both laminated films with a homogeneous alignment of mesogens and a homeotropic one, large movements could be induced by irradiation with UV light at room temperature. A partly laminated film with homogeneous CLCP bent from both ends of the whole film, while one with homeotropic CLCP bent up from the center of the film toward the light source. These results indicate that we enable plastic films with no photoresponsive property to move flexibly upon photoirradiation just by laminating the CLCP layers partly, and the photoinduced motions of the laminated films are completely dependent on the alignment direction of the mesogens in the CLCP layers. In addition, it was found that the maximum stress generated in the films and the stress increment are also different between the homogeneous CLCP laminated films and the homeotropic ones.

Polarization-controlled, photodriven bending in monodomain liquid crystal elastomer cantilevers

We report on the fast and optically controlled angular bending of cantilevers made from liquid crystal polymer networks functionalized with azobenzene moieties (azo-LCN). For potential applications such as adaptive optics, photoresponsive cantilevers should rapidly deform to controlled angles while maintaining a modulus that can accomplish appreciable mechanical work. This work demonstrates cantilevers made of monodomain azo-LCN containing pendant (side chain) azobenzene mesogens with a storage modulus of 1.4 GPa bend 85° in less than 300 ms upon exposure to 442 nm irradiation. Moreover, the bending angle of these monodomain azo-LCN cantilevers can be controlled by the polarization angle of the source relative to the long-axis of the cantilever. The bending performance (deformation angle and speed) of this monodomain system is compared to a polydomain analogue. The impact of azobenzene concentration, laser intensity, and thickness on these parameters is also presented.

Photoresponsive side-chain liquid crystalline polymers with an easily cross-linkable azobenzene mesogen

The synthesis of a series of novel photoresponsive side-chain liquid crystalline polymers (LCPs) bearing an N-hydroxysuccinimide carboxylate-substituted azobenzene mesogen and their use in generating LCP networks are described. The obtained polymers and their monomers were characterized with 1H NMR, UV-vis, TGA, DSC, POM and SAXS techniques. The length of the flexible spacers in the polymers and their monomers show significant influence on their properties such as the phase transition behaviors and the monomer reactivity. The polymerization reactivity of the monomers increases with an increase in the spacer length and only those monomers and polymers with a flexible spacer ≥ (CH2)6 show liquid crystallinity with their mesophases being smectic A. In addition, the polymers have proven to be easily cross-linkable with a difunctional primary amine under mild conditions both in solution and in film, demonstrating that they are very useful precursors for photoresponsive LCP networks. Furthermore, the photoresponsivity of the polymer solution in tetrahydrofuran and the crosslinked polymer film was also confirmed by their occurrence of the UV and visible light-induced trans/cisphotoisomerization.

Novel Mesogenic Azobenzene Dimer at Air−Water and Air−Solid Interfaces

We have synthesized a novel mesogenic azobenzene molecule and studied its monolayer film properties at air-water interface (Langmuir film) and air-solid interface (Langmuir-Blodgett film). The material, H-shaped dimer bis[5-(4'-n-dodecyloxy benzoyloxy)-2-(4''-methylphenylazo)phenyl] adipate (12D1H) exhibits a smectic C phase between 51 and 48 degrees C on cooling. Surface manometry studies showed the formation of a stable monolayer at the air-water interface. Brewster angle microscopy (BAM) showed that liquid domains coexisting with the gas region at large area transformed to a uniform liquid phase with increasing surface density and finally to a collapsed state. We have carried out atomic force microscope (AFM) studies on Langmuir-Blodgett (LB) films transferred onto freshly cleaved hydrophilic mica substrate. The AFM images showed domains of height of about 3.8 nm, which corresponds to the estimated height of the molecule confirming the formation of monomolecular film. On a hydrophobic silicon substrate, the LB transfer yields a bilayer film, which dewets to form uniform nanodroplets of diameter of about 100 nm and height in the range 10-50 nm. Our analysis indicated that the mechanism involved in the formation of nanodroplets can be attributed to spinodal dewetting. The 12D1H molecule containing an azobenzene group undergoes a trans to cis transformation in the presence of ultraviolet light. Our surface manometry studies showed that the monolayer in the presence of ultraviolet light was more stable with a collapse pressure three times that of the monolayer in the dark.