, was isolated, in which the reaction of the two phosphite anions [HPO 3 ] 2À within the {W 18 O 56 } cage could be followed spectroscopically. As well as full X-ray crystallographic analysis, we studied the reactivity of the cluster using both solution-state NMR spectroscopy and mass spectrometry. These techniques show that the cluster undergoes a structural rearrangement in solution whereby the {HPO 3 } moieties dimerize to form a weakly interacting (O 3 PH···HPO 3 ) moiety. In the crystalline state the cluster exhibits a thermally triggered oxidation of the two P III template moieties to form P V centers (phosphite to phosphate), commensurate with the transformation of the cage into a Wells-Dawson {W 18 O 54 } cluster.Polyoxometalates (POMs) are a unique class of metal oxide anions exhibiting a large variety of structural versatility and interesting physical properties, [1][2][3] as well as the ability to show variable redox potentials.[4] Wells-Dawson-type (WD) clusters with a general formula of [W 18 O 54 , etc.) are one of the most widely investigated families of molecules in the POM family.[5] WD clusters are described as rigid nanocages {W 18 O 54 } in which two tetrahedral heteroanions {XO 4 } are embedded and their electrochemistry has been extensively examined.[6] However, the properties of WD clusters are mainly attributed to the multiple redox states of the rigid metal oxide framework. We have successfully manipulated the redox behavior of WD clusters by introducing electronically active heteroatoms into the metal oxide shell. In this respect, a series of novel 4À into a flash memory architecture. [8] This result drove us to the development of a new heteroatom-templated functional system. However, despite this work [7,8] we are yet to obtain direct spectroscopic evidence demonstrating the reactivity of heteroanions "trapped" within a molecular metal oxide polyoxometalate nanocage.Herein, we report a system that allows us to directly probe the transformation of reactive templates within a polyoxometalate nanocage using NMR spectroscopy and mass spectrometry. To do this we designed and synthesized a P . Energy values for the HOMO-LUMO gap (HLG) for compounds 1 a, 2 a, and 3 a are given in eV, and their frontier orbitals are shown in Figure S13. Atom colors: O = red; P = orange; W = dark gray; H = light gray.