Questioning the paradigm of metal complex promoted phosphodiester hydrolysis: [Mo7O24](6-) polyoxometalate cluster as an unlikely catalyst for the hydrolysis of a DNA model substrate.

The first example of a phosphodiester bond cleavage promoted by a highly negatively charged polyoxometalate cluster has been discovered: the hydrolysis of the phosphodiester bond in a DNA model substrate bis(p-nitrophenyl)phosphate (BNPP) is promoted by the heptamolybdate anion Mo7O24 with rates which represent an acceleration of nearly four orders of magnitude compared to the uncatalyzed cleavage.