Water stabilization of Zr₆-based metal–organic frameworks via solvent-assisted ligand incorporation

Abstract

Water stability in metal–organic frameworks (MOFs) is critical for several practical applications; we report here fundamental understanding how capillary forces induce damage to MOFs and highlight that metal node functionalization as a strategy to create vapor-stable and recyclable MOFs.

Postsynthetic Modification of Zirconium Metal‐Organic Frameworks

“…It was later found that NU‐1000 materials containing perfluorinated alkanes (obtained via SALI) demonstrate enhanced water stabilities. The node functionalisation removes the polar terminal OH and H 2 O ligands, which interact strongly with water, while the incorporated fluorinated ligands prevent water from accessing the Zr 6 clusters . Perfluorinated NU‐1000 materials were subsequently loaded with Pd nanoparticles (confined within the pores), and investigated as catalysts for the C–H arylation of indoles in H 2 O…”

A Zirconium Macrocyclic Metal–Organic Framework with Predesigned Shape‐Persistent Apertures

“…Site‐specific substitution with functional groups can be accomplished on both the interior and exterior of macrocycles as well . The coordinating DEF molecules on SBUs could also be replaced by various motifs to perform chemical reactions inside the channels . Taking all the structural features into account, Zr‐MCMOF is promising for displaying special host–guest interactions, which could be useful in separations of structural isomers.…”

Tetrazine‐Based Metal‐Organic Frameworks as Scaffolds for Post‐Synthetic Modification by the Click Reaction

“…It is very difficult to obtain MOFs equipped with large functional groups in their pore structures by direct solvothermal reactions. However, post‐synthetic modification of MOFs have proved to enable addition of functional groups,, increasing the hydrophobicity of the pore structure, or the stability …”