Self‐Organization on Multiple Length Scales in “Hairy Rod”‐Coil Block Copolymer Supramolecular Complexes

A peptide‐synthetic hybrid block copolymer, poly(ethylene oxide)‐block‐poly(L‐glutamic acid), is shown to form supramolecular complexes with primary alkylamines of varying alkyl chain lengths (8 to 18 methylene units) in organic solvents via acid‐base proton transfer and subsequent ionic bonding. The peptidic block being in theα‐helical conformation, these materials behave as coil‐“hairy rod” block copolymers, and show hierarchically self‐organized nanostructures in the solid state. X‐ray scattering measurements show mesomorphic behavior at the length scales of both the overall block copolymer and the polypeptide‐alkylammonium complex. magnified image