Frontiers of Actinides and Metal–Organic Frameworks: Diversifying Metal/Ligand Selection and Probing Radiation Stability

Metal–organic frameworks (MOFs) have developed into a prominent porous materials class through rational design, reticular chemistry, and an emphasis on applied science. While MOF applications continue to manifest and pervade many fields, MOFs are increasingly becoming relevant in matters of fundamental science, and this is especially true when it comes to the actinide elements. The atomic precision and tunability of MOF structures provides a unique opportunity to study the perplexing f-orbital chemistry of the actinide elements, which are pivotal in global energy, security, medicine, and so forth. This dissertation explores several frontiers of MOFs and actinide chemistry: (i) diversifying metal selection, (ii) diversifying linker selection, and (iii) probing radiation stability. The first two frontiers focus on novelty in structural assembly. We unlocked the synthesis of the first plutonium-based MOF and fostered exploration with a softer donor linker in a thorium MOF system. The third frontier pivots from assembly to breakdown with understanding the role of metal selection in MOF radiation stability. These works relied on mastering appropriate materials handling and method development for characterization of alpha-emitting radionuclides. Understandably, there are experimental and material limitations with radioactive samples, and thus, versatile theoretical perspectives were integral to comprehensive evaluations of our actinide MOF systems. An additional theme of understanding periodic trends of tetravalent metals is interwoven throughout to contextualize the works. These efforts at the intersection of the actinides with the MOF platform underscore fundamental actinide science and fortify the viability of MOF applications in high radiation fields.