An unprecedented cobalt(II)-containing Wells–Dawson-type tungstovanadate-based metal–organic framework as an efficient catalyst for ring-opening polymerization of ε-caprolactone.

By utilizing a flexible fluorinated bis(triazole) ligand 1,4-bis(1,2,4-triazole-1-ylmethyl)-2,3,5,6-tetrafluorobenzene (Fbtx), a thermally and chemically stable cobalt(II)-containing tungstovanadate-based metal–organic framework (MOF) {[Co₃(Fbtx)₅(V₂W₁₈O₆₂)(H₂O)₂]·26H₂O}_n (denoted as CZU-5) was synthesized and structurally characterized. The X-ray structural analysis revealed that CZU-5 features a three-dimensional (3-D) self-penetrated α-polonium cubic structure, which results from a 3-D 4-fold interpenetrated diamondoid [Co(Fbtx)]_n network connected by the Wells–Dawson-type tungstovanadate clusters. Unexpectedly, the introduction of vanadium atoms as heteroatoms into the Dawson-type anion in polyoxometalate (POM)-based coordination polymers has not been reported to date. For the first time, the POM-based material was demonstrated to be an effective catalyst for the solvent-free ring-opening polymerization of ε-caprolactone. Moreover, the CZU-5 catalyst could be recycled up to five times with the retention of both catalytic activity and crystal structure. [ABSTRACT FROM AUTHOR]