Chirality on Amorphous High-T_g Polymeric Nanofilms: Optical Activity Amplification by Thermal Annealing

The chiroptical properties of amorphous chiral polymers functionalized with conjugated trans-azoaromatic chromophore linked to the backbone through a chiral cyclic pyrrolidine moiety of one single configuration at the solid state, as thin films, were investigated. For the first time nanometric thin films of amorphous polymers (not liquid crystals) showed a remarkable chiral amplification upon thermal treatment at a temperature close to their T_g. The side-chain azobenzene chromophores rearrangement driven by the enhanced chain mobility seems to favor the formation of nanodomains of conformationally ordered macromolecular chains with one prevailing helical handedness whose optical activity depends on the configuration of the intrinsic chirality of the monomeric units and which as a result are stable at room temperature for a long time.