Brozek, CarlFabrizio, Kevin2023-07-062023-07-06https://hdl.handle.net/1794/28496The emergence of metal-organic frameworks (MOFs) as a class of versatile and renewable materials has instigated a paradigm shift in the field of chemistry. Their exceptional properties, such as high surface area, tunable porosity, and chemical and thermal stability, have garnered intense research interest for a wide range of applications, including gas storage, separation, sensing, and catalysis. Among the expansive library of MOFs, photoredox-active MOFs have gained particular attention due to their ability to reversibly store charges and photocatalytically degrade contaminants – a task necessary in the fight against climate change. However, poor orbital overlap and charge delocalization in most MOFs limit their efficiency in visible-light catalysis. In this dissertation, we explore the idea of improving MOF photocatalyst performance through reversible external stimuli. Each chapter delves into a distinct external stimulus and its effect on the electronic structure of MOFs. We investigate how cations, crystal size, and temperature affect nuclear rearrangements in MOFs, leading to a deepened understanding of how to improve photocatalytic performance. Taken together, this dissertation provides an analysis of the effect of nuclear rearrangement on defining the electronic structure in MOFs, and it lays a foundation for the development of new, highly efficient MOF photocatalysts.en-USAll Rights Reserved.chemistrymaterials scienceMOFsphotocatalysisporous materialsElectronic Thesis or Dissertation