Synthesis of bent-shaped azobenzene main-chain polymers for photo-switching properties

Abstract

This work presents the synthesis of the new bent-core polymers with siloxane units connected to the one side of azobenzene units. The structure of siloxane-based azobenzene bent-core polymers, 7a–c, was elucidated by spectral analysis (nuclear magnetic resonance and Fourier-transform infrared spectroscopy). The results of gel permeation chromatography suggested that all polymers (7a–c) showed polydisperse (polydispersity index >1). Besides, the extent of polymerization in the following order: 7a > 7b > 7c, where the degree of polymerization values were 7, 8 and 11, respectively. Polarizing optical microscopy revealed that the bent-core liquid crystal (BCLC) monomers, 6a and 6b, displayed the smectic A phase, whereas BCLC monomer 6c and all siloxane-based main-chain polymers (MCPs) (7a–c) were crystalline in nature. The result of ultraviolet-visible spectroscopy demonstrated that all MCPs (7a–c) exhibited strong photoisomerization behavior in solution. All polymers (7a–c) showed trans to cis isomerization in about 200 s, whereas the reverse process required much longer times ranging from 400 to 520 min in solution. The photo-switching study on azobenzene containing polymers stated that the effect of alkyl chain length and type of central core units on trans to cis isomerization were negligible. In contrast, both parameters influence the cis to trans process in which the photo-switching behavior of these materials may be primarily suitably exploited in the field of photo-induced phenomenon.