Precisely Designed Difunctionalized Cyclodextrin Produces a Solid‐State Organic Porous Hierarchical Supramolecular Assembly

Regioselective di‐functionalization of a cyclodextrin allows hydrophobic domains to be directed in a geometrically controlled manner. This controlled orientation ultimately gives access to an original hierarchical assembly in the solid state. This assembly spans over three levels of hierarchy which are governed by synergistic host‐guest inclusions, directed hydrophobic effect and hydrogen bonding. This combination of interactions precisely positioned in space through regioselective functionalization of a cyclodextrin creates a porous organic architecture. Hierarchical assembly: A porous hierarchical crystalline network was built using the macrocyclic‐based supramolecular polymerization strategy. The precise di‐functionalization of the α‐cyclodextrin using hydrophobic functions encoded for three different hierarchical levels: a first supramolecular polymer, a second hexameric column and a third trihexagonal packing which ultimately give rise to channel‐like pores.