Synthesis and Photoinduced Anisotropy of Polymers Containing Nunchaku-Like Unit with an Azobenzene and a Mesogen

A series of polymers containing nunchaku-like unit with an azo chromophore and a mesogen group was successfully prepared and photoinduced anisotropy of the obtained polymers was minutely investigated. Firstly, monomers containing nunchaku-like unit with an azo chromophore and a mesogen group linked by flexible group were synthesized. The structure of the monomers was confirmed via NMR COSY spectra. Subsequently, the obtained monomers were polymerized into corresponding polymers through RAFT polymerization. The prepared polymer samples were characterized through NMR, FTIR, gel permeation chromatography (GPC), and UV-vis testing while the thermal properties of the samples were investigated through differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) measurements. The photoinduced isomerization of the polymers, which was researched in situ via measuring UV-vis spectra of the polymer solutions and spin-coated films under irradiation with 450 nm light or putting in darkness, demonstrated the rapid trans-cis-trans isomerization of the polymers. When irradiated with a linearly polarized light, significant photoinduced birefringence and dichroism were observed, suggesting photoinduced isomerization of azobenzene can drive orientation of mesogen in the system. This study blazes a way to design the optical materials with light-controllable birefringence and dichroism.

Photoinduced Anisotropy of IWK-2D Azobenzene Molecular Glassy Films

We have experimentally studied photoinduced anisotropy (PA) of holographic gratings in IWK-2D [precise chemical notation: 2-(3-(4-((4-(bis (2-(trityloxy) ethyl) amino) phenyl) diazenyl) styryl)-5,5-dimethylcyclohex-2-enylidene) malononitrile] azobenzene molecular glassy films in transmission and reflection modes using a special simultaneous holographic recording and readout setups which enabled measurements of PA time evolution. PA manifested itself by diffraction efficiency difference with linear s- and p-polarizations. Three different types of polarization holographic gratings were recorded and studied using p-p, L-L and L-R polarized beams creating different recording interference patterns. Atomic force microscope (AFM) was used to study the surface profile changes. Experimental evidence was obtained that the transmission mode PA was due to the both recorded surface relief and volume polarization gratings whereas the reflection mode PA was due to the recorded surface relief gratings. The main PA features were similar for all three types of polarization gratings whereas details were different. PA properties of IWK-2D films were notably distinctive from those of previously studied films.