Hierarchical assembly of thermoresponsive helical dendronized poly(phenylacetylene)s through photo-crosslinking of the thermal aggregates.

Supramolecular assembly of helical homopolymers to form stable chiral entities in water is highly valuable for creating chiral nanostructures and fabricating chiral biomaterials. Here we report on thermally induced supramolecular assembly of helical dendronized poly(phenylacetylene)s (PPAs) in aqueous solutions, and their in-situ photo-crosslinking at elevated temperatures to afford crosslinked nano-assemblies with hierarchical structures and stabilized helicities. These helical dendronized homopolymers carry cinnamate-cored dendritic oligoethylene glycol (OEG) pendants, which exhibit characteristic thermoresponsive behavior. Their thermal aggregation confers hexagonal packing of the polymer chains, and simultaneously resulting in enhancement of their chiralities. Assisted by radial amphiphilicity and worm-like molecular geometry, these dendronized PPAs form supramolecular twisted fibers, spheroid particles or toroids via thermal aggregation. Through UV photoirradiation above their cloud points (Ts), cycloaddition of cinnamate moieties from the dendritic pendants promotes intermolecular crosslinking of dendronized PPA chains within the thermal aggregates, and simultaneously, the dynamic morphologies and supramolecular chirality from the dendronized PPAs through thermally induced aggregation can be fixed. In addition, photo-crosslinking can be occurred solely within individual aggregates due to the protection of densely packed dendritic OEGs. Therefore, various crosslinked assemblies from the dendronized homopolymers with tailorable morphologies and stabilized chirality are fabricated by tuning their thermally induced dynamic aggregations followed by in-situ photo-crosslinking. We believe that this work paves a convenient route to fabricate chiral assemblies with stabilized morphologies and fixed chiralities from dynamic helical homopolymers through intermolecular crosslinking, which can be promising for various chiral applications.