Heterogeneous postassembly modification of zirconium metal-organic cages in supramolecular frameworks

We report a heterogeneous postassembly modification (PAM) to synthesize a zirconium metal-organic cage decorated with acrylate functional groups, ZrT-1-AA, which cannot be synthesized by direct coordination-driven self-assembly owing to the reactivity and instability of the ligand. The PAM process is carried out in a single-crystal-to-single-crystal transformation under mild reaction conditions with high efficiency, which is confirmed by ESI-TOF-MS and 1H NMR. In addition, ZrT-1-AA is crosslinked into shaped materials to demonstrate its potential applications. The proposed PAM strategy sheds light on the development of Zr-MOCs decorated with reactive functional groups, whose introduction is challenging or impossible via direct self-assembly.