Photoracemization broadening of selective reflection and polarization band of glassy chiral-nematic films

Glass-forming liquid crystals consisting of a cyclohexane central core with (S)-1-phenyl-ethylamine and (4-cyanophenyl)naphthalene pendants were synthesized as hosts for racemizable (R)-dinaphtho2,1-d:1',2'-f]1,3]dioxepin, a chiral dopant. Chiral-nematic films 14, 22, and 35 mum thick were prepared for thermal and photoinduced racemization at temperatures from 95 to 130°C, i.e. in the mesomorphic temperature range, over a period of hours to days. Spatially modulated photoracemization was accomplished with an insignificant contribution from the thermal process at temperatures around 100°C over a period of up to 3 h. With an absorbance per unit thickness of 6.2 mum^-1 at 334 nm, the photochemical process was essentially confined to the irradiated surface, thereby setting up counter-diffusion of the two enantiomers through the film, and hence the pitch gradient as visualized by atomic force microscopy. The significantly widened selective reflection band was interpreted with the Good-Karali theory extended for a gradient-pitch film. Furthermore, the bandwidth was found to increase with decreasing racemization temperature or with increasing film thickness, further validating the presence of a pitch gradient as a result of controlled photoracemization.