Interrogation of actinide-ligand bonds and second-sphere interactions in actinyl bearing hybrid materials
Open AccessThe efforts contained within this dissertation sought to prepare families of interrelated uranyl-bearing (UO22+) hybrid materials, as a means to delineate structure-property relationships and interrogate changes to the underlying electronic and vibronic structure of the prepared phases within a family of materials. By doing so, we aim to explore trends in uranyl bond strengths as a function of altering either the first sphere bonding or second sphere species present. While most phases bear the uranyl dication (UO22+), efforts presented in Chapter 4 expand across the actinide series to produce the neptunyl (NpO22+) and plutonyl (PuO22+) analogs of those reported in Chapter 3. These efforts allow a conversation regarding changes to actinide-ligand bonds across the series, and rationalize observed differences in solid state assembly, in the case of two Pu phases. For our purposes, the hybrid materials in question may be defined as those which contain organic and inorganic (AnO22+ containing) components. We rely on the presence of second-sphere interactions, namely hydrogen or (pseudo)halogen bonds, to assemble these hybrid materials, which contain either an [AnO2X4]2- (An = U, Np, Pu; X = Cl, Br) or [UO2(NCS)5]3- anion at their core. We characterize all phases crystallographically, to assess assembly motifs and interaction distances, followed by a spectroscopic analysis to interrogate the underlying electronic and vibronic structure, and qualitatively assess changes to actinyl bonding. The workflow later evolves into that of a hybrid one, incorporating both experimental and computational analyses to gain a deeper understanding of the bonding landscape, and consider changes to the local coordination environment by way of discussing bond character, composition, and hybridization as a function of changes to either the first and second sphere coordination environment. These efforts have afforded 42 novel compounds, allowing for a discussion regarding the role hydrogen or (pseudo)halogen bonding interactions play on solid-state assembly of actinyl containing materials, and the dynamic interplay these interactions have on observed assembly, properties, and actinide-ligand bond strengths.
- All rights reserved
Notice to Authors
If you are the author of this work and you have any questions about the information on this page, please use the Contact form to get in touch with us.