Tailoring of chiroptical properties of substituted polyanilines by controlling steric hindrance

Optically active polyorthoanisidine, polyorthotoluidine, polyorthoethylaniline and polyorthochloroaniline were synthesized with chemical polymerization of corresponding monomers in aqueous medium by using d- or l-camphorsulfonic acid (d- or l-CSA) as chiral dopant, ammonium persulfate as oxidant, and diaminodiphenylamine as initiator. By circular dichroism spectroscopic measurements, it was found that PANI exhibited generally a reversed chirality in comparison with the used chiral dopant, but the substituted PANIs had the same one as the chiral dopant. This revealed that the substituent at ortho position caused helical inversion of conformation in comparison with the parent PANI. Such effect was further confirmed by the influence of the copolymerization of aniline and its derivatives on the chirality of the copolymers. The effect of the substituent on the chirality of the copolymers was increased with the increase of the steric hindrance of the ortho substituent. A mechanism was proposed to explain the effects of steric hindrance on the chirality of PANIs. The clarified relationship between the steric hindrance and the chirality of the polymer can enable us to tailor the chiroptical properties of functional polymer materials for future application.