Rigid PN Cages as 3-Dimensional Building Blocks for Crystalline or Amorphous Networked Materials

Three-dimensional covalent connectors are valuable synthons for accessing crystalline or amorphous networks. Currently, fused polycyclic alkanes are employed as connectors in this context. We debut phosphorus-nitrogen (PN) cages as new 3-dimensional inorganic connectors that yield crystalline MOFs and amorphous networks that can feature gas porosity. We show that the high tunability of PN cages accelerates network diversification and the presence of a responsive 31P NMR spectroscopic handle provides structural insight. Collectively, this work unlocks a new and convenient high-dimensionality synthon for reticular chemistry.