Metal Coordination Induces Phase Segregation in Amphipolar Arborescent Copolymers with a Core–Shell–Corona Architecture

[Image: see text] Arborescent copolymers with a core–shell–corona (CSC) architecture were synthesized and the topology of the molecules was challenged (constrained) through intramolecular interactions, resulting in phase separation breaking the symmetry of radial density. The inner poly(2-vinylpyridine) shell of these arborescent polystyrene-g-[poly(2-vinylpyridine)-b-polystyrene] molecules can self-assemble by binding metallic salts and acids in apolar and intermediate-polarity solvents. Upon loading with HAuCl(4), the characteristics of the polymer templates govern the “loading sites” of the metal within the molecules. Unique morphologies were observed for the metal-loaded G0–G4 arborescent copolymers investigated, namely, spherical, toroidal, raspberry-like, spherical nanocage, and a new worm-in-sphere morphology. The reason for the emergence of such morphologies is the interplay among intramolecular interactions of unlike polymer segments, solvent selectivity, the entropic elasticity of the arborescent substrate, and phase segregation induced by coordination with the charged metallic species. Meanwhile, the stability of the arborescent molecules against aggregation provides intramolecular phase segregation with imposed “confined” geometry and thus leads to nonconventional morphologies. Furthermore, the size of the arborescent molecules is much smaller than that of other known particles (droplets) serving as confined geometries. Computer simulations were used to model the mesostructure of the arborescent copolymers, to demonstrate the influence of solvent selectivity, together with HAuCl(4) loading, on the evolution of the morphology of the macromolecules.