Regulation of Catenation in Metal-Organic Frameworks with Tunable Clathrochelate-Based Building Blocks

Inherent pore structures and pore environment of metal-organic frameworks (MOFs) have a significant impact on the macroscopic functionalities. In this regard, it is valuable to explore the regulation of catenation and then tune the pore structures and pore environment, optimally at the molecular level. Here we report regulating the catenation of Zn-MOFs based on the primitive cubic (pcu) net, isoreticular to MOF-5, via fine-tuning the clathrochelate-based ditopic building blocks. The use of clathrochelate-based carboxylate ligands with bulky cores of n-butyl groups led to the synthesis of a Zn-MOF with the pcu net, while clathrochelate linkers with relatively fewer bulky cores give a twofold interpenetrated Zn-MOF structure under similar conditions.