Pore Surface Engineering with Controlled Loadings of Functional Groups via Click Chemistry in Highly Stable Metal–Organic Frameworks

Reactions of ZrCl4 and single or mixed linear
dicarboxylic
acids bearing methyl or azide groups lead to highly stable isoreticular
metal–organic frameworks (MOFs) with content-tunable, accessible,
reactive azide groups inside the large pores. These Zr-based MOFs
offer an ideal platform for pore surface engineering by anchoring
various functional groups with controlled loadings onto the pore walls
via the click reaction, endowing the MOFs with tailor-made interfaces.
Significantly, the framework and crystallinity of the functionalized
MOFs are well-retained, and the engineered pore surfaces have been
demonstrated to be readily accessible, thus providing more opportunities
for powerful and broad applications of MOFs.