Zr-Based Metal-Organic Polyhedra as Advanced Functional Porous Platform

The past two decades have witnessed an explosive growth of metal-organic frameworks (MOFs), thanks to the reticular chemistry. Based on a rich choice of building blocks, metal clusters and organic ligands, now more than 110,000 MOF structures have been synthesized. Despite the phenomenal success of MOFs, the molecular counterparts metal-organic polyhedra (MOPs), cage-based porous materials have been significantly under-explored. Because of weak inter-cage interactions, the structual design and applications on MOPs are initially focused on the cage molecules. To our surprise, recently, we have identified notable exceptions in Zr-based MOPs. Unlike other typical MOP series, identical packing structures can be assembled from different functionalized ligands, similar to MOFs. In addition, these MOPs are robust enough to exhibit permanent porosity in the solid state, while they are still soluble in some solvents. Based on the extraordinary dual features, we further investigated the rational design strategies of the solid-state packing of Zr-MOPs. In this presentation, we highlight the extraordinary features of Zr-based MOPs. We expect that these unique dual features of Zr-MOPs can lead to many intriguing applications that are not accessible by typical discrete cages or extended frameworks, bridging the gap between the two communities of porous solids, MOFs and MOPs