Stepwise Hierarchical Self‐Assembly of Supramolecular Amphiphiles into Higher‐Order Three‐Dimensional Nanostructures

Abstract Hierarchical self‐assembly describes the spontaneous formation of large well‐defined molecular structures through a sequence of spontaneous processes driven by noncovalent interactions between molecules and intermediate structures. The chemical information embedded in the initial molecules determines the structural outcome of the overall assembly process. This is clearly advantageous in terms of product accessibility, but poses limits to the extent of control that can be exerted over the process. Here we report the stepwise hierarchical self‐assembly of well‐defined three‐dimensional organic nanostructures with dimensions of over 100 nm in each single xyz‐direction and a total volume of up to 1.5×10⁻² μm³. These structures are formed through three consecutive processes that rely exclusively on the establishment of noncovalent interactions between the components: (1) complex formation between Zn²⁺ and a macrocyclic ligand, (2) association of the amphiphiles in disk‐like micellar structures and, finally, (3) ATP‐induced stacking of the disks into large hexagonal prisms. The top and bottom surface of these structures are flat multivalent cationic surfaces covered with ATP with dimensions in the order of 2×10⁵ nm² onto which nanometer‐sized gold nanoparticles can be deposited through a final self‐assembly process. The stepwise hierarchical process bears a close analogy with a multistep covalent synthetic pathway with the difference that all steps rely exclusively on noncovalent interactions.