Local Electronic Charge Transfer in the Helical Induction of Cis-Transoid Poly(4-carboxyphenyl)acetylene by Chiral Amines

Understanding the phenomena that lead to the formation of a specific helicity in helical polymers remains a challenge even today. Various polymers have been shown to assume different helical screw-senses depending on different stimuli. Acid–base chiral amines, for example, can induce helical conformations on cis-transoid poly­(4-carboxyphenyl)­acetylene yielding high-intensity circular dichroism signals. There have been many experimental attempts to elucidate the driving forces involved, but the induction process remains unclear. Here, we investigate the mechanism of helical polymer formation by both Molecular Dynamics (MD) and Density Functional Theory (DFT) approaches. We find that DFT calculations and the dissociation energies between 4 monomer polymers and amines show a clear trend in the affinity of R and S conformers with clockwise and counterclockwise polymer screw-senses, respectively. The charge analysis revealed that the local charge transfer effect plays a crucial role that leads to the helical polymer-amine induction.