A bowl-to-bowl programmable hierarchical self-assembly into multidimensional superstructures

Bowl-shaped molecular containers (BSMCs) feature anisotropic concave-convex surfaces, yet their pronounced curvature critically hinders intermolecular alignment and directional packing, rendering the controllable construction of ordered supramolecular superstructures a persistent challenge. Here, we introduce a bowl-to-bowl programmable strategy to precisely control the self-assembly of BSMCs into multidimensional superstructures. By programming the binding modes between BSMCs during the formation of secondary building units (SBUs), three distinct binding configurations were achieved: bottom-to-wall dimer, bottom-to-bottom dimer, and wall-to-wall tetramer. Consequently, these SBUs successfully overcame curvature-induced limitations and self-assembled into one-dimensional rod-like (1DRS), two-dimensional layered (2DLS), and three-dimensional diamondoid (3DDS) superstructures, respectively. Notably, the pore volume progressively increases from 1DRS to 2DLS, and ultimately to 3DDS, resulting in a significant enhancement in iodine adsorption capacity.