Solid‐State Hierarchical Cyclodextrin‐Based Supramolecular Polymer Constructed by Primary, Secondary, and Tertiary Azido Interactions

International audience; The crystallization of a di-azido-alpha-cyclodextrin revealed a polymeric self-assembly involving a variety of azido-type interactions. The crystal arrangement relies on the cooperativity of a primary azido inclusion, a secondary azido-azido interaction involving an unprecedented distribution of canonical forms, and a tertiary azido-groove interaction. The second azido group brings in a major contribution to the supramolecular structure illustrating the benefit of a difunctionalization for the generation of hierarchy.