Heterogeneity within Order in Crystals of a Porous Metal–Organic Framework

Generally, crystals of synthetic porous materials such as metal–organic frameworks (MOFs) are commonly made up from one kind of repeating pore structure which predominates the whole material. Surprisingly, little is known about how to introduce heterogeneously arranged pores within a crystal of homogeneous pores without losing the crystalline nature of the material. Here, we outline a strategy for producing crystals of MOF-5 in which a system of meso- and macropores either permeates the whole crystal to make sponge-like crystals or is entirely enclosed by a thick crystalline microporous MOF-5 sheath to make pomegranate-like crystals. These new forms of crystals represent a new class of materials in which micro-, meso-, and macroporosity are juxtaposed and are directly linked unique arrangements known to be useful in natural systems but heretofore unknown in synthetic crystals.