Effect of packing on orientation and cis–trans isomerization of azobenzene chromophore in Langmuir–Blodgett film

Photoactive film material of long-chain azobenzene derivative, p-(ω  -trimethylammoniodecyloxy)-p′p′-octyloxyazobenzene bromide (TAOAB), was fabricated into a Langmuir–Blodgett (LB) film by a polyion-complex technique using poly(sodium 4-styrenesulfonate) as a polyanion. To investigate the effect of the packing state of the azobenzene chromophore on its orientation and cis–trans   isomerization, TAOAB was mixed with methyl stearate in the LB film matrix at various mole fractions (XTAOAB)(XTAOAB), and structural characterizations were subsequently carried out by means of Fourier transform infrared and ultraviolet–visible spectroscopies, X-ray diffraction analysis, and atomic force microscopy. The results obtained show that as the degree of packing increases, both the azobenzene chromophores and the hydrocarbon chains orient more perpendicularly to the surface of the LB film. In addition, reversible cis–trans photoisomerization of TAOAB took place upon alternate irradiation with UV and visible light even in a mixed LB film with the chromophores in a dense lateral packing state. In the process of thermal cis-to-trans   isomerization, we found that the reaction rate is strongly affected by the packing state of TAOAB at 20 °C, reflecting the differences in steric hindrance among LB films of various XTAOABXTAOAB. In addition, higher activation energy was obtained for thermal cis-to-trans isomerization when the free volume around the chromophores became smaller.