Helical Assemblies of One-Dimensional Supramolecular Polymers Composed of Helical Macromolecules: Generation of Circularly Polarized Light Using an Infinitesimal Chiral Source

We report the synthesis of one-dimensional supramolecular polymers composed of one-handed helical macromolecules bearing fluorescent pendant groups and the generation of circularly polarized light on the basis of hierarchical chiral amplification starting from a tiny amount of chiral substituent. Copolymerization of benzo[1,2-b:4,5-b']dithiophene-appended achiral/chiral isocyanides (99:1, mol/mol) with a solid-state photoluminescence feature afforded submicrometer supramolecular fibers, in which almost perfect single-handed helical polyisocyanides were noncovalently connected end to end. The resulting helical supramolecular polymers were further helically assembled to form a cholesteric liquid crystal film with an intense circularly polarized luminescence (CPL) signal. Surprisingly, the supramolecular system containing only 0.01 mol % of the chiral monomer unit also emitted the observable circularly polarized light owing to multiple chiral amplification from an infinitesimal point chirality to helical chirality and then to supramolecular chirality. Furthermore, chiral information was efficiently transferred from the helically assembled supramolecular system containing 1 mol % of the chiral unit to achiral dye molecules blended in the film, allowing full-color tunable induced CPL with luminescence dissymmetry factors greater than 1.0 × 10^-2. This unprecedentedly strong chiral amplification enables the creation of helical supramolecular polymers and chirally assembled systems with various chiral functions based solely on an infinitesimal chiral source.