Peering Into the Solution Behavior of Polyoxometal Nanoclusters

Outcome: Researchers in the Center for Sustainable Materials Chemistry have discovered a new way to study polyoxometal nanoclusters in solution. By following the movement of a Ga13 polyoxocation via 1H-Nuclear Magnetic Resonance (NMR), they have proven the existence of the cluster in solution.  The result is both novel and surprising, as such an inorganic species has not previously been observed and characterized using this NMR technique.

Impacts/Benefits: The synthesis and characterization of polyoxometal cations represents a new frontier in aqueous metal chemistry.  Studying these nanoclusters provides opportunities for designing new electrocatalysts, developing water-based inks for printed electronics and sustainable semiconductor manufacturing, understanding natural water systems, and enabling advances in structural biology.  

Explanation: Until now, single crystal X-ray diffraction was the primary way to obtain structural information on polyoxocationic clusters.  But, this technique is expensive, relies on the availability of crystals,  and only yields information about the clusters in the solid state. By using NMR, researchers are now able to confirm the existence and stability of the nanoclusters in solution. Understanding the integrity and equilibria of polyoxometal clusters, such as Ga13, in solution is integral for downstream processing and predictive synthesis of new and unique clusters.  By combining the NMR technique with small angle-X-ray scattering, Raman spectroscopy, and mass spectrometry, giant strides are being made in understanding the chemistry behind these clusters.