"Self-Adaptive" Coassembly of Colloidal "Saturn-like" Host-Guest Complexes Enabled by Toroidal Micellar Rubber Bands

The creation of inclusion complexes with "Saturn-like" geometries has attracted increasing attention for supramolecular systems, but expansion of the concept to nanoscale colloidal systems remains a challenge. Here, we report a strategy to assemble toroidal polyisoprene-b-poly(2-vinylpyridine) (PI-b-P2VP) block copolymer micelles with a PI core and a P2VP corona and inorganic (e.g., silica) nanoparticles of variable shape and dimensions into "Saturn-like" constructs with high fidelity and yield. The precise nesting of the nanoparticles between the toroidal building units is realized by virtue of hydrogen bonding and self-adaptive expansion of the flexible toroidal units enabled by a flexible, low T_g PI core. Once the toroidal units are cross-linked, the self-adaptive feature is lost and coassembly yields instead out-of-cavity bound nanoparticles. "Saturn-like" assemblies can also be formed along silica nanosphere-decorated cylindrical micelles or, alternatively, at the hydroxyl-functionalized termini of cylindrical micelles to yield colloidal [3]rotaxanes.