Three polyoxometalate-based metal–organic frameworks were synthesized by the thermal reaction of pyridyl-Anderson polyoxometalate linker and lanthanide ions. With the help of [Ru(bpy)3]2+ photosensitizer, these frameworks exhibited excellent photocatalytic sulfide oxidation performance with sulfoxide selectivity. The reactive oxygen species as well as the photooxidation mechanism were also explored.

We successfully designed and obtained a new family of polyoxometalates (POMs) containing mixed-metal elements and a trialkoxyl (TRIS) ligand via a very simple one-pot process under mild condition. Single-crystal X-ray diffraction revealed that this family belongs to compact Lindqvist-type hexatungstovanadates. In particular, the hydroxyl-containing product can be further functionalized through esterification. Not only does this work open a broad door for unusual POM clusters involving vanadium and tungsten atoms in the future, but also the design concept of this work also provides new insight for the synthesis and further exploration of POMs.

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