Timing matters: pre-assembly post-assembly functionalization of a polyoxovanadate-organic cuboid.

The pre-assembly and post-assembly approaches in the functionalization of a polyoxovanadate-organic cuboid, [{VS}(QPTC){V}], are discussed. We have shown that the two pathways have led to distinctly different systems, with either an expanded or contracted interior void space, when phenylphosphonate is introduced at different stages of the self-assembly. One leaves the cuboid framework largely intact, whereas the other results in a compact, twisted cuboid.