Si Wu

Photoinduced reversible gel–sol transitions of dicholesterol-linked azobenzene derivatives through breaking and reforming of van der Waals interactions

A series of new symmetric dicholesterol-linked azobenzene gelators with different spacer lengths have been synthesized. The compounds with spacers of zero, two or six methylene units are denoted as DCAZO0, DCAZO2 and DCAZO6, respectively. A gelation test reveals that a subtle change in the length of the spacer can produce a dramatic change in the gelation behavior of the compounds. DCAZO2 obtains the minimum gelation concentration among the three gelators. For cyclopentanone gel of DCAZO2, the reversible gel–sol transitions by irradiation with UV and visible light are investigated by UV-vis absorption and circular dichroism (CD) spectra, SEM, TEM and XRD analyses. Upon UV irradiation of the gel, trans–cisphotoisomerization of the azobenzene groups occurs, the change in molecular polarity leads to the breaking of van der Waals interactions, resulting in the gel–sol transition. The gel can be recovered by the reverse cis–transphotoisomerization after the exposure to visible light. SEM, TEM and XRD studies reveal that the gelator molecules self-assemble into one-dimensional fibers with diameters 50–100 nm in an anticlockwise direction, which further crossed-linked to form three-dimensional networks.

Supramolecular bisazopolymers exhibiting enhanced photoinduced birefringence and enhanced stability of birefringence for four-dimensional optical recording

Extremely stable, high-density information storage media were prepared by the connection of two azobenzene groups via hydrogen bonding to form supramolecular bisazopolymers. The supramolecular bisazopolymers contain 4-((4-hydroxyphenyl)diazenyl)benzonitrile (AzoCN) as a hydrogen bonding donor and poly(6-(4-(pyridin-4-yldiazenyl)phenoxy)hexyl methacrylate) (pAzopy) as a hydrogen bonding acceptor. High quality films of the supramolecular bisazopolymers pAzopy/(AzoCN)x (x = 0.25, 0.5, 0.75, 1.0) with different molar ratios of donor/acceptor were prepared by spin-casting. The supramolecular bisazopolymers spontaneously form lamellar structures with a periodic thickness of 7.1 nm. These samples exhibit optically induced birefringence. The birefringence and proportion of remnant birefringence increase from 0.0265 to 0.1 and 50.5% to 108%, respectively, as the content of AzoCN in the samples increases, which indicates a larger proportion of AzoCN enhances both the birefringence and its stability. We also use an azopolymer without pyridine groups (pAzoCH3) and AzoCN to do a control experiment, which shows that pAzoCH3/(AzoCN)1.0 do not show significant enhanced birefringence and its stability. The enhancements in pAzopy/(AzoCN)x are because of the unique structure of the supramolecular bisazopolymers. A new laser direct writing system has been developed for optical recording on the azopolymers. The pAzopy/(AzoCN)1.0 film is significantly better at image recording than the pAzopy film, because the optically recorded images on the pAzopy/(AzoCN)1.0 film are very clear after storage for four months whereas the optically recorded images on the pAzopy one disappear after just one day. Four-dimensional optical recording has been achieved by integrating the polarization and the intensity of the laser and the two dimensions of a plane. An information density of about 0.93 Gbit cm−2 could be optically recorded on the pAzopy/(AzoCN)1.0 film, which is about 20 times the information density of a normal DVD.

Optically controllable polarized luminescence from azopolymer films doped with a lanthanide complex

Two azopolymers (DACENO2 and DACEOCH3) with a special structure were designed and synthesized. The azopolymer films doped with the lanthanide complex Eu(TTA)3Phen were prepared by a casting method with a mixed solution of the azopolymer and lanthanide complex. UV-vis spectra show that the absorption peaks of the predesigned azopolymers DACENO2 and DACEOCH3 are separated from that of Eu(TTA)3Phen. Under this circumstance, the photo-induced anisotropy of the films could not be destroyed by excitation and emission during fluorescence measurements. Polarized luminescence of both oriented films was observed with polarization ratios of 3.0 for the DACENO2–Eu(TTA)3Phen film and 2.7 for the DACEOCH3–Eu(TTA)3Phen film at 613 nm, respectively. The luminescent properties of the film were found to be affected by the chemical structure of the azopolymer, the extent of the photo-induced alignment and the angle between the orientated direction of the film and the direction of the polarizer. All the results from this work revealed that the polarized luminescence from the azopolymer film doped with a lanthanide complex can be controlled by the extent of photo-induced alignment.

All-optical fabrication of ellipsoidal caps on azobenzene functional polymers.

We have fabricated an azobenzene (azo) polymer microellipsoidal cap array of hexagonal symmetry with high-power laser ablation and subsequent single-beam-induced mass migration. High-power interference with polarization-controlled triple beams is utilized to inscribe a circular bump array directly on the surface of the azo polymer film. The produced circular cap array is exposed to the linearly polarized beam, and the caps are stretched along the polarization direction of the irradiating beam. A model of gradient force emerged by the interaction of the polarized beam and azo polymer is constructed to explain the mechanism of such polarization-induced microscale shape deformation.

Light driving force for surface patterning on azobenzene-containing polymers

In this paper, we investigated the effect of light driving force induced surface deformation on azobenzene-containing polymers. The surface deformation is attributed to light-induced mass migration inside the polymers. Circular cap arrays are firstly fabricated by high power laser ablation via polarization controlled three-beam interference. The circular caps are subsequently exposed to polarization controlled two-beam interfering field. The results illuminate that when the interfering laser beams are both set to P polarization, the circular caps are deformed. While the laser beams are of other interfering modes like (S, S) and (+45° , -45°), the caps are seldom deformed. The circular caps are also exposed to single intensity-homogeneous linearly polarized laser beam. The deformation of the caps keeps the same direction as the irradiating polarization. A model based on the focusing effect of the circular caps is addressed to explain the origin of the light driving force for mass migration in azopolymers. The all-optical approach for the production of deformed caps can be used to generate aspherical lens, which may be applied to many domains.