Supramolecular Interactions as glue for the design of smart architectures

Weak interactions such as π-π, CH-π, H bonds and VdW forces, play a key role in the rational design of new fascinating supramolecular materials. In effect these interactions are able to drive the self-assembly of simple building blocks to create well defined molecular polyhedra. These materials have attracted much attention not only for their infinite range of application but also thanks to their very interesting supramolecular architectures. Here we present how 72 H-bonds guide the assembly of two kinds of hexagonal molecular tiles in a quasi-truncated octahedron q-TO (which corresponds to one of the 13 Archimedean solids)1 and how different counterions (BF4-, PF6- or NO3-, CF3SO3-) can largely modulate the structure of hexameric toroidal supramolecules h-SP which, at higher hierarchical level, can assembly in sphere2. Both q-TO and h-SP crystallize in high symmetric cubic space groups and both present a void volume inside the macrostructure: q-TO have a 2200Å3 of free total volume and it exhibits the remarkably ability of encapsulate a large assortment of molecular species as solvent molecules and organic guests; h-SP shows a permanent porosity with 18000 Å3 of void space and it is a good material for the adsorption of gases such as CO2 or solvent vapors. Porous dipeptide-based crystals held together by hydrogen bonds and showing selective adsorption of CO2 vs N2 are also presented.3