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- Title
Following the Reaction of Heteroanions inside a {W<sub>18</sub>O<sub>56</sub>} Polyoxometalate Nanocage by NMR Spectroscopy and Mass Spectrometry.
- Authors
Zheng, Qi; Vilà-Nadal, Laia; Busche, Christoph; Mathieson, Jennifer S.; Long, De-Liang; Cronin, Leroy
- Abstract
By incorporating phosphorus(III)-based anions into a polyoxometalate cage, a new type of tungsten-based unconventional Dawson-like cluster, [W18O56(HPIIIO3)2(H2O)2]8−, was isolated, in which the reaction of the two phosphite anions [HPO3]2− within the {W18O56} 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 {HPO3} moieties dimerize to form a weakly interacting (O3PH⋅⋅⋅HPO3) moiety. In the crystalline state the cluster exhibits a thermally triggered oxidation of the two PIII template moieties to form PV centers (phosphite to phosphate), commensurate with the transformation of the cage into a Wells-Dawson {W18O54} cluster.
- Subjects
PHOSPHORUS; POLYOXOMETALATES; TUNGSTEN; X-ray crystallography; NUCLEAR magnetic resonance spectroscopy; MASS spectrometry
- Publication
Angewandte Chemie, 2015, Vol 127, Issue 27, p8006
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201502295