2018, Toshchevikov, Vladimir, Petrova, Tatiana, Saphiannikova, Marina

Azobenzene-containing polymer networks are unique compounds that are able to change their shape in response to light, which makes them prospective materials for photocontrollable nano-templates, sensors, microrobots, artificial muscles, etc. In present work, we study the kinetics of light-induced ordering and deformation in two-component polymer networks containing optically inert liquid crystalline (LC) mesogens and azobenzene chromophores. By this, we generalize our previous theory [J. Phys. Chem. Lett. 2017, 8, 1094–1098] devoted to the kinetics of photoizomerization in one-component azo-polymers without mesogenic inclusions. The kinetic equations of photoisomerization are used, taking into account the angular selectivity of the photoisomerization with respect to the polarization direction of the light E. After multiple trans-cis-trans photoisomerization cycles, the azobenzenes are reoriented preferably perpendicular to the vector E. This changes the ordering of the mesogens due to the orientational LC interactions between the components. The light-induced reordering is accompanied by network deformation. Time evolution of ordering and deformation is found as a function of the intensity of light and structural parameters of the LC azo-networks, which define the viscosity, the strength of the LC interactions between the components, the volume fraction of the azobenzene moieties, and the angular distribution of azobenzenes in polymer chains. Established structure-property relationships are in agreement with a number of experimental data.

2023, Toshchevikov, Vladimir, Saphiannikova, Marina

Azobenzene-containing polymers (azo-polymers) have been a subject of extensive investigations during the last two and half decades, due to their remarkable ability to undergo pronounced alignment and deformation under irradiation with light. The molecular ordering and deformation in azo-polymers of various structures under irradiation with linearly polarized light was described in a series of theoretical works, based on the effect of the reorientation of azobenzene moieties due to the anisotropic character of the photoisomerization processes. In the present study, we generalize the previous orientation approach to describe the photo-alignment and deformation of azo-polymer networks under irradiation with elliptically polarized light. We demonstrate that, in general, the light-induced ordering and deformation have a biaxial symmetry defined by the polarization ellipse. Azobenzene chromophores have a tendency to align along the direction of light propagation, the orientation in the other two directions being dependent of the aspect ratio of the polarization ellipse. This causes deformation of azo-polymer networks along the direction of light propagation, the sign of which (expansion/contraction) is defined by a chemical structure of network strands. Theoretical results are in agreement with experiments and have a practical importance to predict the photo-mechanical response of azo-polymers depending on their structure and on the polarization of light.