From Sergeants and Soldiers to Chiral Conflict Effects in Helical Polymers by Acting on the Conformational Composition of the Comonomers

Different communication mechanisms can be switched within a copolymer by acting on the conformational composition of the components and their chirality. Thus, a sergeant and soldiers effect is produced in two diastereomeric copolymer series, poly[(S)‐1r‐co‐(S)‐2(1−r)] and poly[(R)‐1r‐co‐(S)‐2(1−r)], owing to the presence in chloroform of a preferred conformation in (S)‐2, and a conformational equilibrium in 1, where a P helix is induced independently of the absolute configuration of the soldier. In THF, the presence of a conformational equilibrium at the pendants of the two components produces a reciprocal chiral enhancement effect by copolymerization of the two monomers, while in DMF, a third chiral to chiral communication switch is produced due to the presence of a single conformer at the pendant group of the two components. In such a case, a chiral conflict or chiral accord effect is produced depending if the two components induce the same or the opposite helical sense. A complete set of communication mechanisms (chiral‐to‐chiral sergeants and soldiers, chiral coalition, chiral conflict, chiral accord, synergistic chiral enhancement) can be activated in a chiral copolymer by acting on the conformational composition and the absolute configuration of the components.