Induction of chirality into a fully sulfonated poly(methoxyaniline) via acid-base interactions with chiral amines

A wide range of chiral amines and amino alcohols associate with poly(2-methoxyaniline-5-sulfonic acid) (PMAS) in aqueous solution, from which optically active PMAS·(amine) films can be cast. The chiral induction is believed to be initiated by acid-base interactions with “free” sulfonic acid groups on the PMAS chains. Chiral amine:PMAS dimer molar ratios as low as 1:4 give PMAS·(amine) films with similar optical activity to those cast from 1:1 molar mixtures, indicating that only one in four of the “free” sulfonate groups on the PMAS chains need to be electrostatically bound by chiral ammonium ions to achieve optimal chiral induction. Circular dichroism studies show that the enantiomeric amines (R)-(+)- and (S)-(−)-1-phenylethylamine induce the opposite helical hands for the supermolecular assemblies of PMAS chains. However, there is no clear correlation between the sign of the CD signals for the PMAS·(amine) films and the configuration of structurally diverse amines.