Side-chain functionalized supramolecular helical brush copolymers

We report poly(isocyanide)-based random copolymers (co-PIC) featuring alkoxycarbonyl-based side-chains synthesized via the metal-catalyzed controlled polymerization of chiral and achiral isocyanide monomers. The pyridine-functionalized achiral monomer provides functional sites while the chiral monomer drives the formation of a one-handed preferred helix. The side-chain functionalized helical polymer undergoes self-assembly with palladated pincer ligands, as evidenced by H-1 NMR and UV-Vis spectroscopies. Circular dichroism (CD) spectroscopy confirms that the side-chain self-assembly does not affect the backbone helicity. We construct supramolecular helical brush copolymers via the metal coordination of the co-PIC backbone with telechelic poly(styrene)s. H-1 NMR and UV-Vis spectroscopies confirm the metal coordination, and CD measurements suggest that the backbone retains its helical conformation. Additionally, viscometry measurements verify the formation of high molecular weight polymers while dynamic light scattering confirms the increasing hydrodynamic radii of the resulting supramolecular brush copolymers. Our methodology constructs complex 3D materials with fully synthetic, secondary structure containing building blocks. We view this as a platform for building architecturally controlled 3D supramolecular materials with high degrees of complexity.