A family of supramolecular frameworks of polyconjugated molecules hosted in aromatic nanochannels

Self-organization of tris-o-phenylenedioxycyclotriphosphazene with a variety of linear π-conjugated molecules resulted in crystalline nanostructured adducts of exceptional stability. Linear conjugated molecules that contain various chains of building blocks (i.e., double bonds, phenyl and thiophene rings) could be included to form the adducts. The polyconjugated molecules were encapsulated in infinite nanochannels lined with aromatic groups, which offer tailored surroundings of weak interactions. The conjugated molecules are sustained by a diffuse network of CH•••π and π •• π interactions that, through cooperation, improve the robustness of the supramolecular adducts. The stabilizing interactions were recognized by using advanced high-resolution 2D hydrogen–carbon solid-state NMR techniques, which allowed to to localize, with rare accuracy, the hydrogen atoms involved in weak hydrogen-atom–π interactions and elucidate the dynamics of large supramolecular assemblies.