Construction and Multiple Exterior Surface Functionalization of Giant Molecular Cages

Abstract

AbstractBy a one‐pot reaction strategy and a stepwise fragment‐coupling approach, three types of giant cage molecules with a triangular prism shape and an approximate cavity volume of 930 Å3 were synthesized. Through efficient aromatic nucleophilic substitution reactions of chlorotriazine with functionalized amines or aliphatic substitution reactions of the linking imino moieties with allyl bromide, the giant cages were successfully functionalized on the surface with multiple hydroxy, 2‐pyridyl, or allyl groups. As evidenced by variable‐temperature 1H NMR spectroscopy, the D3h‐ and C3v‐symmetric cage molecules underwent very slow conformational changes or deformation in solution because of their giant size and their flexible building units. Their giant cavities, different electronic interiors, and facile multiple exterior surface functionalization could render the molecular cages powerful three‐dimensional macrocyclic hosts that might find wide applications in supramolecular science.