Investigating the autocatalytic self-assembly of Keggin-based polyoxometalate clusters

David Lockey
Many areas of chemistry strive towards the directed synthesis of complex molecules. Polyoxometalates (POMs) are discrete metal oxide clusters that span a wide area of chemistry and are often topologically complex or interesting. They can be formed from many different atom types and in many different reaction conditions and can include a range of inorganic and organic complexes within their structures. Their variable structures and functions have led to use in many areas of chemistry, most
more » ... y catalysis. The way that the formation of discrete clusters is achieved is still largely unknown and is often called "self-assembly". An investigation into the kinetics of the Keggin type POM was looked at using a UV/Vis detection-based system in order to find the underlying kinetics of the reaction. This revealed an underlying autocatalytic formation system in which the Keggin catalyzes its own formation, providing vital further insight into how these clusters are formed in situ. Also, the synthesis of the largest known POM, the Mo368, was looked at. Notoriously difficult to synthesize based on literature conditions, the goal was to improve the synthesis in order to obtain high quality single crystals of the cluster. A better understanding of the synthesis of the largest POM cluster would allow for further clarity into the exact conditions and could provide insight into the sort of reaction equilibria needed to form even larger structures. This was achieved by employing a robotic liquid handling platform for high accuracy synthesis. Specific areas of synthesis were targeted, and the reaction conditions changed depending on the results of previous reaction runs.
doi:10.5525/gla.thesis.82677 fatcat:ov2suzgtnbfllpfvr3aafxeww4