Photoisomerization Of Azobenzene Units Research Articles

Surface relief structures for light coupling at air/liquid interface

Relief patterns were photoinduced on the surface of a thin film floating on water. The structures have a length of several millimeters with a width of 33 μm. Both the intensity and the polarization of the irradiated light change the characteristics of the generated patterns. The light induced structuration is the result of simultaneously a reversible material transport originated by photoisomerization of azobenzene units and a process of self-organization of the molecules. The structures were used as waveguide or grating to couple light at the air/liquid interface on a short or long distance. The fabrication of waveguides can be extended to any liquid substrates.

Scissor-Shaped Photochromic Dyads: Hierarchical Self-Assembly and Photoresponsive Property.

Unique relationships between hierarchically organized biological nanostructures and functions have motivated chemists to construct sophisticated artificial nanostructured systems from small and simple synthetic molecules through self-assembly. As one of such sophisticated systems, we have investigated scissor-shaped photochromic dyads that can hierarchically self-assemble into discrete nanostructures showing photoresponsive properties. We synthesized various azobenzene dyads and found that these dyads adopt intramolecularly folded conformation like a closed scissor, and then self-assemble into toroidal nanostructures by generating curvature. The toroids further organize into nanotubes and further into helical supramolecular fibers depending on the nature of alkyl substituents. All of these nanostructures can be dissociated and reorganized through the photoisomerization of azobenzene units. On the other hand, the introduction of stilbene chromophores instead of azobenzenes leads to one-dimensional supramolecular polymerization, which upon the intramolecular photocyclization of stilbene chromophores shifts to curved self-assembly leading to helicoidal fibers with distinct supramolecular chirality.

Photoinduced Reversible Morphological Transformation of Azobenzene-Containing Pseudo-2D Polymers.

2D polymer sheets containing azobenzene are successfully prepared by a facile strategy of "2D self-assembly polymerization (2DSP)" via free radical polymerization in solution. A bola amphiphile containing azobenzene as a novel monomer is designed and synthesized. The results indicate that single-layer covalent pseudo-2D polymers on a micrometer scale are obtained after polymerization with vinyl monomers. Moreover, the 2D polymer sheets are highly sensitive to UV light due to incorporation of azobenzene groups into the polymer. Upon alternative irradiation with UV and visible light, the morphological transformation between sheets and rolled-up nanotubes can be achieved based on the reversible trans-to-cis photoisomerization of azobenzene units in the 2D polymer sheets.

Tuning and Erasing Surface Wrinkles by Reversible Visible‐Light‐Induced Photoisomerization

AbstractPeriodic wrinkling across different scales has received considerable attention because it not only represents structure failure but also finds wide applications. How to prevent wrinkling or create desired wrinkling patterns is non‐trivial because the dynamic evolution of wrinkles is a highly nonlinear problem. Herein, we report a simple yet powerful method to dynamically tune and/or erase wrinkling patterns with visible light. The light‐induced photoisomerization of azobenzene units in azopolymer films leads to stress release and consequently to the erasure of the wrinkles. The wrinkles in unexposed regions are also affected and oriented perpendicular to the exposed boundary during the stress reorganization. Theoretical models were developed to understand the dynamics of the reversible photoisomerization‐induced wrinkle evolution. This method can be applied for designing functional materials/devices, for example, for the reversible optical writing/erasure of information as demonstrated here.

Three-Component Supramolecular System with Multistimuli-Responsive Properties in Water.

Hyperbranched polyethylenimine terminated with isobutyramide groups (HPEI-IBAm), 4-(phenylazo)benzoic acid (PABA), and α-cyclodextrin (α-CD) were assembled together at pH≈7 to form the three-component supramolecular complexes that were verified by (1) H and 2D ROESY (1) H NMR spectroscopy. UV/Vis spectrometric titration experiments showed that the content of α-CD in the three-component complexes was less than the feed amount and it was difficult for all the PABA units in the complexes to further form complexes with α-CD. The obtained three-component supramolecular complexes exhibited thermoresponsive properties in water. Increasing the α-CD concentration led to a sharp increase in the cloud point temperature (Tcp ) at the beginning, but after the [α-CD]/[PABA] ratio was in the region of 1.3-1.6, the Tcp increased gradually When the concentration of α-CD was low, a higher concentration of PABA led to a lower Tcp , however, the opposite was observed when the concentration of α-CD was high. For the three-component complex, increasing the α-CD concentration at pH≈7 or at pH≈9 led to different Tcp temperatures. In the low α-CD concentration range, adjusting the pH from ≈7-≈9 resulted in an increase in the Tcp , similar but not so pronounced as that of the two-component system of HPEI-IBAm/[PABA]. When the concentration of α-CD was high, adjusting the pH from ≈7-≈9 decreased the Tcp ; this observation is different to that of the two-component system of HPEI-IBAm/[PABA]. Reversible trans-to-cis photoisomerization of azobenzene units in the complexes occurred, following irradiation with UV or visible light. Trans-to-cis isomerization of azobenzene units decreased the Tcp . However, this result differed to that of the two-component system of HPEI-IBAm/PABA.

Photoresponsive structure transformation and emission enhancement based on a tapered azobenzene gelator

Due to trans-to-cis photoisomerization of azobenzene unit, an enhanced fluorescence via J-aggregate molecular arrangement can be observed.

Surface pattern based on an azobenzene-containing copolymer thin film and its light-driven morphology modulation

A type of azobenzene-containing block copolymer polymethyl methacrylate-b-poly (n-butylmethacrylate-co-6-(4-(phenylazo) benzoate) hexyl methacrylate) (PMMA-b-(PnBMA-co-PAzoMA)) was synthesized by the atom transfer radical polymerization (ATRP). Macroinitiator polymethyl methacrylate (PMMA) was prepared by ATRP and used to initiate the copolymerization of monomern-butyl methacrylate (nBMA) and azobenzene-based methacrylate monomer (AzoMA). Herein, three block copolymers with different molecular weights and block volume fractions were obtained and spin-coated on a silicon substrate or quartz plate before annealing at 180 °C for 14 h. The surface morphologies in these annealed copolymer films were observed by atomic force microscopy (AFM). Bicontinuous stripe or island patterns with different sizes were formed dependent on the film thickness. These ordered patterns are considered to be formed arising from the dewetting process of the surface layer in the copolymer film. Photoisomerization of azobenzene units in the copolymer films changed the dewetting behaviors of the surface layer of the thin film. Therefore, some copolymer annealed films showed a reversible morphology conversion between bicontinuous stripe and island structure when exposed to UV light and upon being stored in the dark. It was found that the composition of the block copolymer had obvious influences on the photoinduced morphology conversion behaviors in these copolymer thin films. When the volumes of PnBMA and PAzoMA phases in the block copolymer were large enough, the surface morphology could be modulated by UV light irradiation and storage in the dark. This work proposes a new possibility for photoinduced control and design of the dewetting processes of thin films using a linear block copolymer.

Near-infrared light induced fusion and fission of azobenzene-containing polymer vesicles

Fusion and fission of azobenzene-containing vesicles doped with Fe3O4 nanoparticles (MN) were induced by irradiation of NIR light. Detailed study shows that photoisomerization of azobenzene units would make the fission process easier, although both behaviours of the vesicles can be solely caused by the photothermal effect of the nanoparticles.

Thermo-, pH-, and Light-Responsive Supramolecular Complexes Based on a Thermoresponsive Hyperbranched Polymer.

Hyperbranched polyethylenimine terminated with isobutyramide groups (HPEI-IBAm) was mixed with 4-(phenylazo)benzoic acid (PABA) to form supramolecular complexes through the neutralization reaction between the amino groups of HPEI-IBAm and the carboxylic acid group of PABA, which was verified by 1H and 2D NOESY 1H NMR spectroscopy. The obtained supramolecular complexes with a molar ratio of PABA to HPEI-IBAm of ≤8 were soluble in water and exhibited thermoresponsive properties. Their cloud point temperature (Tcp) was sensitive to PABA content, and PABA molecules were exchanged between HPEI-IBAm hosts. The topology of the polymer affected the change in Tcp of the complexes. At pH ∼7, increasing the PABA content decreased Tcp, whereas it caused Tcp to increase at pH ∼9. Reversible trans-to-cis photoisomerization of azobenzene units in the complexes occurred following irradiation with UV or visible light. At pH ∼7, trans-to-cis isomerization of azobenzene units increased Tcp, whereas the opposite occurred at pH ∼9.

Self-Assembly and Photoresponsive Behavior of Amphiphilic Diblock Copolymers Containing Azobenzene Moieties

An amphiphilic diblock copolymer, poly(ethylene oxide)-block-poly {6-[4-(4-ethoxyphenylazo)phenoxy] hexyl methacrylate}, was synthesized using atom transfer radical polymerization. In the solution of tetrahydrofuran and water, the diblock copolymer formed micrometer scale vesicles by self-assembly. Under the irradiation of UV light at 365 nm, these microvesicles generated such photoresponsive behavior as photoinduced expansion, swelling and fusion due to trans-cis photoisomerization of azobenzene units. The self-assembled vesicles even enlarged to be about five times their original size because of photoinduced fusion.

Photo-responsive perylene diimid–azobenzene dyad: Photochemistry and its morphology control by self-assembly

A new type of photo-responsive perylene diimide–azobenzene dyad (PDI–AZO) was synthesized by covalently adjoining azobenzene chromophore to N-imide position of perylene diimide. The optical properties, photoisomerization and self-assembly morphology of the resultant composites were characterized by UV–vis absorption, photoluminescence (PL) spectra and scanning electron microscope. Larger one-dimension nanobelts were observed in self-assembly PDI–AZO due to the strong molecule stacking. The red-shifted bands arise from the larger conjugation extension by π-electron overlap of perylene ring and azobenzene chromophore. The spectral changes upon the irradiation of ultraviolet light show that larger conjugation extension does not significantly affect the photochromism rate, but it retards the further photoisomerization of azobenzene units in PDI–AZO. The PL quenching of PDI–AZO is dominated by the transfer of the excitons before reverting to the ground state accompanied by the radiation due to the larger conjugation extension.