Coordination and Photoisomerization of Azobenzene-Amino Acid Schiff Base Copper(II) Complexes to Lysozyme

In this study, we exhibited an amino acid (arginine and threonine) derivative Schiff base copper(II) complexes incorporating an azobenzene moiety as a photoresponsive site and conjugated it to egg white lysozyme, a well-known protein, to change ligand conformation under binding to lysozyme. Among several spectroscopic investigations, ESR clearly showed that the nitrogen atom of the amino acid residue of lysozyme was bound to the paramagnetic copper(II) ion of the complex, and UV light irradiation confirmed photoisomerization of the azobenzene moiety of the ligand to cis-form. The binding mode was considered by means of spectroscopic as well as computational methods, whereas complete crystallographic verification was still a preliminary stage.

SYNTHESIS AND CHARAOTERIZATION OF NOVEL THERMOTROPIO LIQUID ORYSTALLINE POLYESTERS BEARING NONLINEAR OPTICAL AZOBENZENE SIDE GROUP

A series of novel thermotropic liquid crystalline polyesters bearing nonlinear optical azobenzene side group were synthesized by high temperature solution polycondensation and their structures,thermal stability, phase transition behavior and crystallinity were characterized by IR,elemental analysis, TG-DTA, polarizing optical microscope (POM) equipped with a hot stage and X-ray diffraction techniques. The results demonstrate that all the synthesized polyesters exhibit nematic liquid crystalline phases and show relatively high glass transition temperatures and good thermal stability.

Synthesis and Crystal Structure of a Novel Chiral 1-Methylpropargyl Ester Carrying Azobenzene Moiety

A novel chiral methylpropargyl ester containing azobenzene moiety（S）-（-）-3-methyl-3-{4-[4-（n-octyloxy）phenylazophenyl]carbonyl}oxy-1-propyne 3（C25H30N2O3,Mr = 406.51） was synthesized and characterized by IR,NMR and single-crystal X-ray diffraction.The crystal is of monoclinic system,space group P21 with a=6.7610（17）,b=7.675（2）,c=22.749（7）,β=97.613（6）°,V=1170.1（6）3,Z=2,Dc=1.154,F（000）=436,μ=0.076 mm-1,R=0.0544 and wR=0.1569 for 2444 observed reflections with Ⅰ〉2σ（Ⅰ）.Structure analysis proved that the azobenzene presents a trans form, and intermolecular hydrogen bonds yield a 3D framework. The ehiral acetylene carrying azobenzene moieties can be a potential alternative nonlinear optical, helical polymer, and liquid crystalline material.

PHOTOINDUCED BIREFRINGENCE AND NUMERICAL SOLUTION OF A NEW DYNAMIC MODEL IN AN AMORPHOUS COPOLYMER CONTAINING AZOBENZENE GROUPS

Photoinduced birefringence is investigated in a new amorphous copolymer containing azobenzene groups. The levels of birefringence signal are found to depend an the polarization angle between the pump beam and the probe beam, and on the ellipticity of the pump beam. Both the growth and decay processes of the birefringence signal can be described by known biexponential equations. The rate constants and the amplitudes associated with the growth process of the photoinduced birefringence are observed to display a linear dependence with the pump beam intensity. A new dynamic model of the photoinduced birefringence is presented taking into account the contributions of both the bans and cis isomers of azobenzene groups and the local polymer segments. The numerical treatment of this model shows good agreement with the experimental data in the whole writing-erasing processes of the photoinduced birefringence conducted in our polymer samples.

Preparation and Photochemical Behavior of a Cationic Azobenzene Dye-Montmorillonite Intercalation Compound

Montmorillonite/cationic azobenzene dye（p-（δ-triethylammoniobutoxy）-p＇-methyl- azobenzene bromide） intercalation compounds were prepared by the conventional ion exchange method. As compared with that of pure cationic azo-dye, the thermal stability of the intercalated dye was greatly enhanced, and the absorption band corresponding to azobenzene group in intercalated dye shifted towards longer wave length by 38 nm. This could be ascribed to the strong conjugation of cationic azo-dye supramolecular order structure（J cluster） confined in a nanoscale space of montmorillonite interlayer gallery. UV/vis spectra data show that the intercalated azo dye in the montmorillonite interlayer space exhibited reversible trans-to-cis photoisomerization and daylight cis-to-trans back reaction. FTIR indicates the successful intercalation of cationic azo-dye into the montmorillonite interlayer.

Isolation and Crystal Structure of Trans-2,2',4,4'-tetramethyl-6,6'-dinitro Azobenzene

Trans-2,2?,4,4?-tetramethyl-6,6?-dinitro azobenzene (C16H16N4O4, Mr = 328.32) was isolated from benzene extract of the leaves of Aconitum sungpanense Hand. Mazz. as a new compound, and characterized by spectral methods and X-ray diffraction analysis. It crystallizes in monoclinic system, space group P21/c with a = 8.544(1), b = 13.997(2), c = 7.161(1) ? ?= 112.97(1), V = 788.4(2) ?, Z = 4, Dc = 1.383 g/cm3, F(000) = 344 and ?MoKa) = 0.102 mm-1. The final R = 0.0395 and wR = 0.1140 for 1913 independent reflections with Rint = 0.0109 and 1329 observed reflections with I > 2s(I). The molecule is composed of two phenyl rings through trans N=N.

Synthesis of azobenzene-containing liquid crystalline gelator for use in liquid crystal gels

A liquid crystalline gelator containing the azobenzene chromophore was synthesized for the first time; it was used to form self- assembled network in nematic liquid crystals resulting in liquid crystal gels with distinct features.

Effect of spacer length on the liquid crystalline property of azobenzene-containing ABA-type triblock copolymers via ATRP

The effect of flexible spacer length on the liquid crystalline property of ABA-type triblock copolymers containing azobenzene groups was investigated. For the study, the monomers, n-[4-(4-ethoxyphenylazo)phenoxy]alkyl methacrylates with varying methylene groups (n = 0, 2, 6) were used to synthesize a series of azobenzene-containing amphiphilic triblock copolymers PAnC–PEG–PAnC by atom transfer radical polymerization (ATRP). Differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and one-dimensional X-ray diffraction (1D WAXD) have shown that the glass transition temperatures of these copolymers decreased with increasing n, PA0C–PEG–PA0C has no mesophase, while both PA2C–PEG–PA2C and PA6C–PEG–PA6C have a nematic mesophase. These differences derive from the length of spacer groups between the polymer backbone and side-chain LC monomers.

POLYMER SCAFFOLDS BEARING AZOBENZENE-POTENTIAL FOR OPTICAL INFORMATION STORAGE

The fundamental optical storage mechanism of the laser light eddressable azobenzene moiety is briefly introduced.A modular and flexible synthesis design furnishes polyester matrices covalently integrating cyanoazobenzene in regularlyspaced side chains. Thin films of these materials are particularly well suited for holographic storape. Notable figures of meritsof liquid crystalline polyesters are response time to blue-green laser light of the order of nanoseconds, storage capacityexpressed as 5000 lines/mm, and high, permanent (almost nine years) diffraction efficiency of the order of 50% or greater,and erasability, The implications of the main chain nature for polyester morphology and for the permanency of the inducedanisotropy are discussed, The design and methods of preparation of other significantly different polymer scaffolds supportingcyanoazobenzene are elaborated. Oligopeptides always result in amorphous materials, whereas copolymethacrylates anddendritic or hyperbranched polyesters provide some materials that exhibit liquid crystallinity. However, none of these scaffolds affords materials that result in permanent anisotropy when exposed to interfering laser light.

Fabrication of azobenzene-functionalized porous polymers for selective CO_(2) capture

Many solid adsorbents have been prepared for the CO_(2)capture.In particular,the photoresponsive adsorbents have attracted extensive interests because of their tunable pore structure and variable responsive behaviors provoked by the external light.However,it is challenging to fabricate the photoresponsive adsorbents featured the big CO_(2)capacity and high CO_(2)selectivity.Herein,copolymerized between 4-phenylazobenzoyl chloride,2,4,6-trichloro-1,3,5-triazine and melamine,a series of azobenzenefunctionalized porous polymers(PTM-AZOs)are successfully synthesized.The PTM-AZOs are verified in possession of proper pore structures,large surface area and photoconductive properties through a series of characterization.The PTM-AZO-2 with the trans-isomerization exhibits the best CO_(2)adsorption amount of 2.7 mmol·g^(-1)(273 K and 0.1 MPa),while the CO_(2)/N_(2)selectivity can reach 2459 and 607 on the trans-and cis-isomerization,respectively.The regulatable pore structures controlled by the photoresponsive azobenzene groups affect the CO_(2)capture performance of the PTM-AZOs.

Facile Synthesis of Amidines via Intermolecular Reductive Coupling of Nitriles with Azobenzene Promoted by Samarium Diiodide

The intermolecular reductive coupling of nitrites with azobenzene induced by SmI2 was studied. Amidine derivatives were prepared in good yields under neutral and mild conditions.

Azobenzene‑Based Solar Thermal Fuels:A Review

The energy storage mechanism of azobenzene is based on the transformation of molecular cis and trans isomerization,while NBD/QC,DHA/VHF,and fulvalene dimetal complexes realize the energy storage function by changing the molecular structure.Acting as“molecular batteries,”they can exhibit excellent charging and discharging behavior by converting between trans and cis isomers or changing molecular structure upon absorption of ultraviolet light.Key properties determining the performance of STFs are stored energy,energy density,half-life,and solar energy conversion efficiency.This review is aiming to provide a comprehensive and authoritative overview on the recent advancements of azobenzene molecular photoswitch system in STFs fields,including derivatives and carbon nano-templates,which is emphasized for its attractive performance.Although the energy storage performance of Azo-STFs has already reached the level of commercial lithium batteries,the cycling capability and controllable release of energy still need to be further explored.For this,some potential solutions to the cycle performance are proposed,and the methods of azobenzene controllable energy release are summarized.Moreover,energy stored by STFs can be released in the form of mechanical energy,which in turn can also promote the release of thermal energy from STFs,implying that there could be a relationship between mechanical and thermal energy in Azo-STFs,providing a potential direction for further research on Azo-STFs.

SYNTHESIS AND CHARACTERIZATION OF POLYMERS BEARING AZOBENZENE AND CARBAZOLE GROUPS VIA POST-AZO-COUPLING REACTION

A series of polymers bearing azobenzene and carbazole groups for photorefractive purpose were prepared viapost-azo-coupling reaction.The successful reaction was identified by spectroscopic analysis and gel permeationchromatography.This approach is more facile compared with the direct polymerization of corresponding functionalmonomer.The polymers prepared have weight average molecular weight of higher than 1.5×10~4 and are easily soluble incommon organic solvents like chloroform and tetrahydrofuran,polymer films with high optical quality could be easilyfabricated through solution casting.Glass transition temperature (T_(?)) of the polymers ranges from 60℃ to 182℃,dependingon the alkylene spacer length between the functional side group and the polymer backbone,and the polymers are relativelystable under 300℃.

OPTICAL PHASE CONJUGATION RESPONSE OF PHOTOINDUCED POLYMER FILMS CONTAINING AZOBENZENE MOIETIES WITH CHIRAL GROUP

An optically active monomer containing azobenzene moieties with chiral group (s-2-methyl-butyl), 4-[2-(methacryloyloxy)ethyloxy] -4'-(s-2-methyl-1-butyloxycarbonyl) azobenzene (M1) was synthesized. Polymer (PM1) possessing optical phase conjugated response was obtained by homopolymerization of the optically active monomer (M1) using free radical polymerization. The polymer was very soluble in common solvents and good optical quality films could be easily fabricated by spin coating. The optical phase conjugated responses of the polymer PM1 were measured by degenerate four-wave mixing (DFWM). In comparison with polymer containing no chiral group, it was found from the preliminary measurement of photoisomeric change that optical phase conjugated response of the PM1 in the long-range order hexagonal symmetry microstructure could be easily controlled by choosing the appropriate polarization direction of the irradiating beams (514.5 nm) and the irradiating number, presumably due to the chiral group in the PM1 molecular structure. For the case of the polymer investigated here, a chiral group side chain was introduced to increase optical phase conjugated response intensity with different polarization directions of the irradiating beams, which aims originally at searching for a new photoactive material.

Preparation of a cationic azobenzene dye-montmorillonite intercalation compound and its photochemical behavior

Montmorillonite/cationic azobenzene dye （GTL） intercalation compounds were prepared by the conventional ion exchange method. As compared with that of pure GTL, the thermal stability of the intercalated GTL was greatly enhanced, and the absorption band corresponding to azobenzene group in intercalated GTL shifted towards a longer wavelength by 55 nm, which could be ascribed to the strong conjugation of GTL supramolecular order structure （J cluster） confined in a nanoscale space of montmorillonite interlayer gallery. The microstructures of the resulting intercalation compounds could be successfully controlled by varying the amount of dye loaded as evidenced by the basal spacing of the intercalation compounds. The intercalated azo dye in the montmorillonite interlayer space exhibited reversible trans-to-cis photoisomerization and thermal cis-to-trans reaction. FTIR proved the successful intercalation of GTL into the silicate layer.

Trans-cis photoisomerization of azobenzene by n→π* excitation:A semiclassical dynamics study

A realistic dynamics simulation study is reported for the trans-cis photoisomerization of azobenzene triggered by the n →π^＊ excitation and the results show that the formation ofcis isomer follows the rotational motion around the N=N bond. The simulation find that the CNN bond angle bending vibrations also play a significant role in the vibronic coupling between the HOMO and LUMO, which essentially leads a nonadiabatic transition of the molecule to the electronic ground state.

DESIGN AND STUDY OF NEW AZOBENZENE LIQUID CRYSTAL/POLYMER MATERIALS

Discussion is presented on the use of the photoisomerization of azobenzene chromophore in the design andpreparation of novel functional materials. The two systems reviewed are azobenzene polymer-stabilized liquid crystals andazobenzene elastomers. In the first case, a polymer network containing azobenzene moieties is used to optically induce andstabilize a long-range liquid crystal orientation without the need of treating the surfaces of the substrates. This optical andrubbing-free approach was applied to nematic and ferroelectric liquid crystals. In the second case, an azobenzene side-chainliquid crystalline polymer is grafted onto a styrene-butadiene-styrene triblock copolymer to yield a photoactive thermoplasticelastomer. Coupled mechanical and optical effects make possible the formation of dimaction gratings that may be useful formechanically tunable optical devices.

Rectifying effect of heterojunction fabricated in freestanding thin film of polyaniline containing azobenzene side-chain

An innovative heterojunction is fabricated between two sides of a freestanding thin film of HCl-doped polyaniline （PANI） derivative containing azobenzene side-chain, which is synthesized through an N-alkyl-substituted reaction. of the film, the side with being irradiated by UV light during preparation is represented as ＇A side＇; the other side without being irradiated is represented as ＇N side＇. The electrical properties of the heterojunction are measured and the rectifying effect is observed in the current voltage characteristic curves with the values of rectifying ratio （30 being 20 at ±0.06 V at T = 77 K and 4 at ±0.02 V at T = 300 K separately.

Theoretical Investigation of Nonlinear Optical Properties of Organicand Transition Metal Hybrid Azobenzene Dendrimers

In this work, we report a theoretical exploration of the responses of organic azobenzene dendrimers. The polarizabilities, the first and second hyperpolarizabilities of the azobenzene monomers （GO）, and the first, second and third generation （G1, G2 and G3, respectively） are investigated by semi-empirical methods. The calculated results show that the nonlinear optical （NLO） properties of these organic dendrimers are mainly determined by the azobenzene chromospheres. Additionally, the values oft and y increase almost in proportion to the number of chromophores. On the other hand, two types of transition metal hybrid azobenzene dendrimers （core-hybrid and branch-end hybrid according to the sites combined with transition metals） are simulated and discussed in detail in the framework of time-dependent density functional theory （TDDFT）. The calculated results reveal that the NLO responses of these metal dendrimers distinctly varied as a result of altering the charge transfer transition scale and the excitation energies.