Journal of the American Chemical Society, Vol.133, No.25, 9872-9877, 2011
Chiral Optical Films Based on Achiral Chromophore Guests
Films constituted by an achiral host polymer and an achiral guest chromophore, which exhibit intense chiral optical responses for both host and guest peaks in the infrared as well as in the UV-visible regions, have been obtained. Such films can have any thickness from the nanoscale up to the macroscopic scale. This unexpected chiral optical behavior is easily achieved by crystallization of a robust commercial stereoregular host polymer (syndiotactic polystyrene, s-PS) from the amorphous phase as induced by a nonracemic guest, followed by exchange of the nonracemic guest with the achiral guest, leading to the formation of polymer-host/chromophore-guest cocrystalline phases. This finding opens the possibility to achieve s-PS-based films with chiral optical response at selected wavelengths. It has been also found that the chiral optical cocrystalline phase of s-PS with azulene exhibits a monoclinic delta-dathrate form with equal proportions of left- and right-handed helices. This confirms that the observed chiral optical behavior arises by the nonracemic native morphology of the crystalline regions, which has been induced by the temporary nonracemic guest.