Splicing Them Together: Construction of Polyoxovanadate–Organic Polyhedra‐Based Pyrgoscages and Catenanes

Abstract Following the construction schemes of pyrgoscages and catenanes, attempts to splice polyoxovanadate‐based metal–organic polyhedra (POV‐MOPs) together have been carried out in this work. To meet the requirements of POV‐MOPs with varied sizes, synthetic strategies including reconstruction of original vertex, introduction of exogenous vertex, and initiative of polyhedral interlock have been developed, which successfully integrated a pair of tetrahedral monomers into an hourglass‐shaped dimer. On top of this, several structuring principles, such as anisotropic enhancement, electrostatic potential reduction, and sufficient intramolecular support, can be drawn from here and popularized to the related MOP systems. Thanks to the advent of such splicing techniques managed by both covalent and non‐covalent interactions, the close communication of POV‐MOPs has afforded not only the unprecedented structural archetypes, but the unique behaviors for NH 3 adsorption as well.