Brendan T. McGrail This dissertation examines the mechanisms that lead to the formation of actinyl peroxide cage clusters, the mechanism of aggregation of actinyl peroxide cage clusters, the photochemical generation of actinyl peroxide complexes in nonaqueous solution, and the electronic structure of the neptunyl peroxide cluster {Np 24 }. In order to study the formation mechanism of {U 24 } I have also developed spectroscopic and mass spectrometric methods to characterize these clusters in

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... tion. Actinyl peroxide cage clusters have been the subject of synthetic efforts by a number of groups since the single crystal structures of the first isolated clusters appeared in 2005. Herein, the mechanism by which one of these clusters, 24-({U 24 }), assembles in solution is examined in detail. Speciation data from electrospray ionization-mass spectrometry is complemented by X-ray diffraction, kinetic analyses, Raman spectroscopy, and small-angle X-ray scattering (SAXS), enabling a full description of the formation mechanism and the role of each reagent. Using this mechanistic understanding, a rational synthesis of the cluster is developed and the iv Chapter 3: Electrospray Ionization Mass Spectrometry Characteriztion of {U 60 } and {U 24 }26 3.1 Electrospray Ionization Mass Spectrometry of Polyoxometalates (POMs) .