Partial‐Interpenetration‐Controlled UiO‐Type Metal‐Organic Framework and its Catalytic Activity

Abstract

An unprecedented correlation between the catalytic activity of a Zr‐based UiO‐type metal‐organic framework (MOF) and its degree of interpenetration (DOI) is reported. The DOI of an MOF is hard to control owing to the high‐energy penalty required to construct a partially interpenetrated structure. Surprisingly, strong interactions between building blocks (inter‐ligand hydrogen bonding) facilitate the formation of partially interpenetrated structures under carefully regulated synthesis conditions. Moreover, catalytic conversion rates for cyanosilylation and Knoevenagel condensation reactions are found to be proportional to the DOI of the MOF. Among MOFs with DOIs in the 0–100% range, that with a DOI of 87% is the most catalytically active. Framework interpenetration is known to lower catalytic performance by impeding reactant diffusion. A higher effective reactant concentration due to tight inclusion in the interpenetrated region is possibly responsible for this inverted result.

Reticular Rare-Earth Metal–Organic Frameworks with High Stability and Defective Sites: Post-Functionalization for Hydrogen Peroxide Detection

“…The ligand configuration plays a pivotal role in determining the formation of metal cluster moieties, as well as topology of the resulting frameworks . It is reported that the introduction of bulky substituents at the 2- and 2′-positions on the biphenyl-4,4′-dicarboxylate ligand, allows one to tune the Zr 6 cluster connectivity and framework topology under appropriate conditions. , Particularly, the Me 4 -BPDC 2– ligand was employed to build PCN-700 featuring the bcu topology. In this ligand, two carboxyl groups are noncoplanar, which link two 8-connected Zr 6 clusters with alternative orientations .…”