Photoinduced alignment of polymer liquid crystals containing azobenzene moieties in the side group VII. On He-Ne laser beam irradiation

Photoinduced alignment in a polymer liquid crystal prepared from 6-{1-[4-(2-cyano-4-nitrophenylazo)phenyl]piperazino}hexyl acrylate and 4'-[6-(methacryloyloxy)hexyloxy]-4-cyanobiphenyl was investigated for the first time on irradiation with a polarized He-Ne laser beam at 633 nm. The azobenzene moieties as well as the inert cyanobiphenyl mesogenic units were aligned with the molecular long axis perpendicular to the polarization direction of the irradiation light. Alignment induced on short irradiation was reversible, while that induced under prolonged irradiation was irreversible due to the occurrence of crosslinking which might be caused by photoinduced decomposition of the azobenzene moieties during the photoirradiation process.     

Photoinduced liquid crystal alignment by layer-by-layer ultrathin films with dual photoreaction moieties

A novel layer-by-layer (LBL) film containing dual photoreaction groups, cinnamoyl and azobenzene, was prepared from poly(diallyldimethylammonium chloride) (PDDA) and a photosensitive polyanion, PCAzo, in aqueous solution via electrostatic attraction. The film was able to induce uniform alignment of liquid crystals (LCs) with good stability and 2.3° pretilt angle by oblique irradiation with linearly polarised ultraviolet light (LPUVL). UV absorption and FTIR spectroscopic results indicate that the photoreactions of the two photoreactive groups jointly participate in generating the anisotropy of the film. The dichroic ratio of the film was found to depend on the number of adsorbed layers. The thicker film has the larger dichroic ratio after the LPUVL irradiation. The reorientation behaviour of the LC molecules was found to be associated with the LBL film thickness. Experiment results revealed that the photo-crosslinking of the cinnamoyl groups was responsible for the stability of the anisotropic orientation, and the isomerisation of the azobenzene chromophores led primarily to the appropriate pretilt angle.     

Photoinduced supramolecular chirality in amorphous azobenzene polymer films

Supramolecular chirality was optically induced in amorphous and achiral azobenzene polymer films by irradiation of a laser beam with elliptical polarization. The chirality resulted from helical orientation of azobenzene chromophores by a combined process of circular and linear polarization. The helix-handedness could be controlled by incident light-handedness.     

Photoresponsive peptoid oligomers bearing azobenzene side chains

N-Substituted glycine peptoid oligomers were synthesized to incorporate a photoresponsive azobenzene side chain. The ability of this side chain to undergo reversible photoisomerization was established, and the cis- to trans-azobenzene thermal isomerization of this side chain was investigated. Circular dichroism studies indicated that trans- to cis-azobenzene isomerization does not significantly alter the backbone conformation in a series of peptoids thought to have well-defined structures.     

On the explanation of the biphotonic processes in polyesters containing azobenzene moieties in the side chain

An explanation for the recently observed biphotonic transitions in side-chain polyesters with azobenzene moieties is given on the basis of experimental observations from optical and Fourier-Transform infrared absorption spectra. We present for the first time experimental evidence that a red laser beam at 633 nm causes cis-trans (Z—E) transitions in azobenzene.     

Photoinduced chirality in achiral liquid crystalline azobenzene polymers containing different polar side groups

Circular dichroism (CD) was induced in the films of two achiral liquid crystalline polymers, poly[(4′-(6-(methacryloyloxy)hexyl)oxy)-(4-X)azobenzene] (PM6X, X = C and N for cyano and nitro, respectively), by irradiation with one handed circularly polarized light (CPL) at 442 nm. The CD and UV spectra of the polymeric films suggest that left-CPL induces a left helical structure and right-CPL reverses the resulting structure into a right helix. For PM6C, the photoinduced CD values of the nematic film are much higher than in the casting and isotropic film. The photoinduced chirality of PM6C films is higher than PM6N due to a higher polarity of nitro groups in PM6N. The PM6N’s CD intensity around 450 nm is increased with the irradiation time of linearly polarized light (LPL) followed by left-CPL irradiation. The correlation between azobenzene chromophores and circularly polarized light will be discussed in the paper.     

Photoinduced conformational changes of azoaromatic polyaspartates containing octadecyl side chains

Copolymers of p-(phenylazo)benzyl-L-aspartate and n-octadecyl-L-aspartate exist as right- and left-handed α-helices in solution at 25°C depending on the copolymer composition: the reversal of helix sense from a right- to left-handed one occurs with increasing the azobenzene content. The α-helices of the copolymers are very sensitive to trifluoroacetic acid (TFA), and are converted into random coil below 2.0% of TFA. Among the copolymers, the copolymer containing 47% azobenzene groups is unique since it exhibits a TFA-induced conformational change from right-handed α-helix to random coil via left-handed α-helix. Upon UV light irradiation at 25°C, the copolymers containing 68 and 89% azobenzene groups caused the reversal in helix sense from a left- to right-handed one. The conformations of the copolymers were dependent on temperature, mostly right-handed and left-handed α-helices at lower and higher temperatures, respectively. On this basis, the copolymer containing 47% azobenzene groups could be made to undergo a photoinduced helix reversal at high temperatures.     

Methylacrylate polymers with photochromic side chains containing heterocyclic sulfonamide substituted azobenzene

Methylacrylate monomers containing azobenzene groups with heterocyclic sulfonamide: sulfisomidyne (4-amino-N-[2,6-dimethylpyrimidyn-4-yl]benzenesulfonamide) and sulfamethoxazole (4-amino-N-[5-methylisoxazol-3-yl]benzenesulfonamide) substituents were synthesized. The monomers were used for preparation of homopolymers and copolymers with butyl 2-methylacrylate and 2-ethylhexyl acrylate. The materials obtained showed photochromic properties manifested by trans-cis isomerization of the side chain azobenzene fragments induced by illumination with unpolarized and polarized light. The decrease of the absorbance of the E(trans) form at ≈450 nm was observed and the materials tested were in form of thin films deposited onto glass.The isomerization of the polymers carried out during ellipsometric measurements showed the reversibility of the process in repeated illumination cycles with green laser light. The change of refractive index caused by illumination was in the range ≈0.005-0.008 as determined by ellipsometry.     

Photomodulation of the chiroptical properties of new chiral methacrylic polymers with side chain azobenzene moieties

We have investigated the photoinduced optical properties of a new class of chiral methacrylic polymers characterised by the presence in the side chain of an optically active pyrrolidinyl ring linked to a trans-azoaromatic system. The homopolymers are enantiomerically pure and their strong optical activity indicates that the macromolecules assume, both in solution and in solid thin films, highly homogeneous conformations with a prevailing chirality. As expected, the studied polymers exhibit reversible linear dichroism and birefringence when irradiated with linearly polarised light. By irradiating with circularly polarised light, we have discovered that it is possible to photomodulate the chiroptical properties of the polymer films. After irradiation with L-polarised light, the CD spectra of the films show a net inversion of their relative sign. The effect is reversible and the original shape of the CD spectra can be restored by pumping with R-polarised radiation. This unexpected new phenomenon can be explained in terms of the ability of the L-polarised radiation to invert the prevailing helicity of the polymeric chains. The observed effect seems to open new possibilities for the use of azobenzene-containing materials as chiroptical switches.     

Bragg-type polarization gratings formed in thick polymer films containing azobenzene and tolane moieties

Holographic gratings were formed in thick polymer films containing azobenzene and diphenylacetylene (tolane) moieties in the Bragg regime. Amorphous polymers containing various contents of the azobenzene moiety with photosensitivity and the tolane moiety with large birefringence in the side chain were synthesized, and optically transparent thick polymer films were prepared. The films were irradiated with a linearly polarized beam from an Ar+ laser (488 nm), and the transmittance of a He-Ne laser beam (633 nm) through a pair of crossed polarizers, with the film between them, was measured to estimate a photoinduced birefringence (deltan). The value of deltan increased with an increase in the tolane moiety content in the polymer films. When two linearly polarized beams at 488 nm were interfered in the film, a diffraction beam was observed, and the maximum diffraction efficiency (eta) increased with the tolane moiety content. In the film containing 70 mol% of the tolane moiety, the highest eta of 99% was achieved, and angular selectivity due to Bragg diffraction was clearly observed. We consider the cooperative molecular motion of the tolane moieties to be induced by the photoinduced change in alignment of the azobenzene moieties even if the polymers show no liquid-crystalline phase. When two orthogonal circularly polarized beams were allowed to interfere in the film, a Bragg-type polarization grating was formed. It was found that the value of eta reached 90% within 920 ms.     

Synthesis and characterisation of polymethacrylates containing para-, meta- and ortho-monosubstituted azobenzene moieties in the side chain

Three sets of novel side-chain liquid crystalline polymers with monosubstituted azobenzene moieties in the side-chain have been studied. These are poly(p-(4′-methoxy-4-oxyhexyloxy azobenzene) benzyl methacrylate) (PPHABM), poly(m-(4′-methoxy-4-oxyhexyloxy azobenzene) benzyl methacrylate) (PMHABM) and poly(o-(4′-methoxy-4-oxyhexyloxy azobenzene) benzyl methacrylate) (POHABM). The chemical structure of the monomers was confirmed by ¹H NMR, ¹³C NMR spectroscopy and elemental analysis. The structural characterisation of the polymers was performed by ¹H NMR spectroscopy and gel permeation chromatography, and their phase behaviour and liquid crystalline properties were studied using differential scanning calorimetry, polarised optical microscopy and wide-angle X-ray diffraction. The results show that the transitional behaviour of side-chain liquid crystalline polymers containing monosubstituted azobenzene moieties depends strongly on the position of the substituent on the azobenzene moiety; for example, the ortho-monosubstituted polymers do not form liquid crystalline phases, but all the para- and meta-monosubstituted polymers exhibit a smectic A phase. Furthermore, the glass transition temperature (T_g ) of the polymers decreases in the order, para > meta > ortho. For the PPHABM and PMHABM polymers the isotropic temperature (T_i ) and liquid crystalline range (ΔT, from T_g to T_i ) are found to be in the order, para > meta, although it is surprising that the associated enthalpy changes in these polymers is the opposite order, meta > para.     

Relationship of photochemical and dynamic behavior of an amorphous photochromic polymer containing azobenzene moieties in the side group

An amorphous copolymer with photochromic azobenzene moieties in the side chain is investigated by UV/Vis and real time dielectric spectroscopy. The aim of this study is to monitor both the reversible E/Z isomerization of the dyes and the influence of the photoreaction onto the matrix. The change of the absorbance and of the dielectric function is measured for the E/Z and the Z/E isomerization. To compare the results model functions are fitted to the measured data and the obtained parameters compared for both experiments. So a correlation between the two spectroscopic methods is established. This analysis leads to a model of the molecular mechanism which is based on excess free volume generated by the photoreaction.     

Synthesis and characterization of a new disubstituted polyacetylene containing indolylazo moieties in side chains

A new disubstituted polyacetylene with indolylazo moieties in its side chains ( 9 ) was synthesized by a post functionalization strategy, which was difficult, or perhaps impossible, to obtain from the direct polymerization of its corresponding monomer. The polymer is soluble in common solvents and thermally stable. The polymer shows good optical transparency with an absorption maximum at 393 nm and a band edge at ～530 nm. Its poled film exhibits a resonant d₃₃ value of 17.9 pm/V and its optical nonlinearity is resistant to thermal decay at up to 147 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5672–5681, 2006     

Photoinduced alignment of azobenzene side‐chain polymers with short spacer: Biaxial orientation and fast response

Side‐chain azobenzene‐containing liquid crystalline polymer (ALCP) of Poly(6‐[4‐(4‐cyanophenylazo)phenoxy] x‐methylene methacrylate)(Px, x is 2 or 6) was synthesized and used to study its photoinduced alignment behavior irradiated by a linearly polarized laser at room temperature. The relationships between transmittance and irradiation time as well as transmittance and various incident angles were studied in detail. The oversaturation phenomenon of P ₂ film was found to be higher than 1 mW/cm² under irradiation energy density. A model of the biaxial orientation was introduced to explain the phenomenon: it is the rigid short spacer that makes it possible for mesogen to coexist in a way of out‐of‐plane and in‐plane orientation (biaxial orientation), in which the type of photoinduced motions is a single mesogen motion in the film of P ₂ , whereas in the film of P ₆ with longer spacer, the motion is a microdomain motion. The whole domain motion restricted the out‐of‐plane orientation, which shows a slow orientation rate and all mesogens aligned within the film plane. A novel dynamic fitting was also presented to describe the orientation of P ₂ , which was discussed in terms of the fitting parameters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1378–1384, 2006     

Surface arrangement of azobenzene moieties in two different azobenzene‐derived Langmiur–Blodgett films

An investigation of two different Langmuir–Blodgett (LB) films, [4‐(6‐oxo‐hexacarboxylic acid)‐3‐trifluoromethyl‐azobenzene] (FAzo5COOH) and copolymer poly{2‐hydroxyethylmethacrylate}₉‐co‐{6‐[3‐((trifluoromethyl)phenyl)azo] phenoxylhe‐Xylmeth‐acrylate}₁(PHEMA‐co‐PFAzoPHA) films, is reported. The different structural behavior of the two types of films was first analyzed in detail by UV–visible spectroscopy. The different wettability of the films under UV–visible irradiation was subsequently studied by the contact‐angle technique. A large change of the contact angle (CA) was observed on PHEMA‐co‐PFAzoPHA films compared to the FAzo5COOH films before and after UV irradiation. The films were finally characterized by atomic force microscopy (AFM), and the morphologies were observed under UV–visible irradiation. The results indicate that the molecules are densely packed in the FAzo5COOH films compared to the PHEMA‐co‐PFAzoPHA films. It is attributed to the strong interaction between neighboring azobenzene moieties in the FAzo5COOH LB films of the smaller molecules. Copyright © 2006 John Wiley & Sons, Ltd.     

Liquid crystalline homopolyesters having main chain calamitic mesogens and one or two side chain azobenzene moieties in the repeat units

Combined semi-rigid homopolyesters, containing both main chain calamitic mesogens and one or two side chain azobenzene units separated by aliphatic (hexamethylene, octamethylene and decamethylene) chains in the polymer repeat units, were prepared and their liquid crystalline properties characterized. Polyesters having two side chain azobenzene units and a main chain biphenyl moiety showed a higher ordered smectic B or smectic F phase, whereas the other polymers containing a main chain 2,5-diphenyl-1,3,4-thiadiazole unit and one or two side chain methoxyazobenzene units formed a smectic C phase despite the presence of different mesogens in the main and side chains. This is probably due to the compact molecular chain-packing and intra- and intermolecular interactions between the polymer backbones and the two azobenzene units.     

Synthesis of conjugated polymers with azobenzene moieties in the main chain

Poly(phenylenevinylene)‐based conjugated polymers with azobenzene groups in the main chains were prepared by the Pd‐catalyzed coupling polymerization of divinylarenes with dihaloarenes. The Pd‐catalyzed coupling polymerization of 4,4′‐divinylazobenzene with dihaloarenes such as 1,3‐dibromobenzene, 1,4‐dibromo‐2,5‐dihexylbenzene, 4,4′‐dibromoazobenzene, and 4,4′‐diiodoazobenzene resulted in polymers with poor solubility. In contrast, soluble polymers containing azobenzene moieties in the main chains were attainable from divinylbenzenes with 4,4′‐dihaloazobenzenes if either or both of the monomers possessed hexyl groups on the aromatic rings. The number‐average molecular weight of the polymer exceeded 10,000 under optimized conditions, and the polymer showed a remarkably redshifted absorption in the visible region (456 nm). ¹H NMR and IR spectra supported that the polymers having only trans‐geometry for the double bonds. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1057–1063, 2000     

Synthesis of polymers bearing proline moieties in the side chains and their application as catalysts for asymmetric induction

Novel polyphenylacetylene and polystyrene derivatives carrying L ‐proline moieties at the side chains were synthesized by the rhodium‐catalyzed and radical polymerizations of the corresponding monomers. The polyphenylacetylene derivatives showed Cotton effects at the absorption region of the main chain, indicating that the polymers adopt helical conformations with predominantly one‐handed screw sense. The polymers catalyzed the asymmetric aldol reactions of acetone with aromatic aldehydes, and cyclohexanone with p‐nitrobenzaldehyde. The enantioselectivities largely depended on the reaction conditions. In the asymmetric aldol reaction of acetone with aromatic aldehydes, the R‐enantiomeric products were predominantly obtained except the cases with the polymer catalyst in CHCl₃. The ee of the products became higher as the reaction temperature was decreased. The polymeric catalysts were recoverable from the reaction mixture by filtration, and the recovered ones catalyzed the asymmetric aldol reaction of acetone with p‐nitrobenzaldehyde without decreasing the product yield and ee. The ee was improved using the copolymers of L ‐proline‐based and nonchiral monomers as catalysts. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Cross-linking-induced permanently perpendicular helix orientation in surface-grafted polyglutamate films

Using a chemical cross-linking procedure, surface-grafted polyglutamate films with a permanently perpendicular helix orientation were prepared. A surface-grafted alpha-helical polyglutamate film containing polymerizable side groups was synthesized by ring-opening terpolymerization of 50 molar% gamma-methyl-L-glutamate N-carboxyanhydride (NCA), 30% gamma-stearyl-L-glutamate NCA and 20% gamma-4-vinylbenzyl-L-glutamate NCA initiated from a silicon substrate functionalized with primary amino groups. The average tilt angle of the end-grafted helices in this film is approximately 66 degrees , indicating a nearly parallel helix orientation with respect to the substrate surface. After swelling of the grafted terpolyglutamate film in stearyl methacrylate and subsequent radical cross-linking, the average helix tilt angle decreases to about 11 degrees, indicating an almost perpendicular helix orientation. The film thickness increases accordingly from 151 A before to approximately 390 A after cross-linking. Extensive solvent treatment of the cross-linked film shows that the perpendicular helix orientation is permanent.