Helix-Sense-Selective Polymerization of Achiral Monomers for the Preparation of Chiral Helical Polyacetylenes Showing Intense CPL in Solid Film State.

Polymer-based circularly polarized luminescent (CPL) materials have attracted ever-increasing interest. However, to construct CPL materials from achiral monomers is still a big challenge. Here, a series of chiral helical substituted polyacetylenes are prepared by helix-sense-selective polymerization (HSSP) of achiral acetylenic monomers (achiral monomer + fluorescent monomer). HSSPs are accomplished in a bi-solvent mixture consisting of chloroform and chiral α-pinene (chiral component). Chirality transfers from the chiral component to the helical copolymers during polymerization, thereby endowing the copolymers with helical chirality. The resulting copolymers are then fabricated into blend films which exhibit intense optical activity and CPL. The monomer ratio and the physical state of the copolymers have significant impacts on their chiroptical and CPL properties. The maximum luminescence dissymmetry factor of the blend films can be up to 1.3 × 10-2 . The universality of the established strategy for exploring polymer-based CPL materials is demonstrated by using different achiral fluorescent monomers. The present work opens a novel alternative for developing CPL-active polymeric materials starting from achiral monomers.