Polyoxometalate research featured in Chemistry in Australia
Six of one, ten of another
New research on the synthesis of polyoxometalates was recently published in the journal Angew. Chemie. and will be highlighted in the April edition of the RACI magazine, Chemistry in Australia.
Polyoxometalates are an expansive class of molecular metal oxides predominantly synthesized in aqueous media by acid-driven condensation of early transition metal oxyanions in their high oxidation states. In this collaborative project involving researchers from the University of Melbourne, Monash University, Umeå University and CSIRO, non-aqueous, microwave-assisted reaction conditions were utilized in the targeted synthesis of two novel molybdovanadates from metastable octamolybdate and decavanadate precursors.
An extensive experimental investigation revealed preferential substitution patterns of vanadium and molybdenum within [V7Mo3O28]3-and [V3Mo3O16(C5H9O3)]2- with the relative population of the structural isomers supported by dispersion-corrected DFT calculations. Excellent agreement between experiment and theory in the study of [V3Mo3O16(C5H9O3)]2- is proposed to be due to a “locking-mechanism” where condensation of the tripodal ligand to the polyanion surface eliminates dynamic post-synthesis solution chemistry. Ongoing research includes elaboration of the pendant organic functionality of these molecules for their incorporation into advanced materials for a variety of applications.
The paper is "Non-Aqueous Microwave-Assisted Syntheses of Deca- and Hexa-Molybdovanadates" by Spillane S., Sharma R., Zavras A., Mulder R., Ohlin C. A., Goerigk L., O'Hair R. A. J. and Ritchie C. Angew. Chemie., 2017,10.1002/anie.201608589.