Hendon, ChristopherMancuso, Jenna2021-11-232021-11-232021-11-23https://hdl.handle.net/1794/26864Metal-organic frameworks (MOFs) have a rich chemistry characterized by a diverse assortment of organic and inorganic components supplemented by post-synthetic modification procedures. The application of a given framework can be dependent on the linker or node chemistry, the pore space, or the combined properties of each. Using experimental data as a starting point or for benchmarking purposes, density functional theory (DFT) calculations are invoked to understand the physical and electronic origins of functional MOF behaviors such as electronic conductivity, catalytic activity, and gas uptake. The size and geometry of inorganic nodes are found to be the dominant factor in determining to what extent charge is localized within individual linkers or nodes, as does the distance between them and their orientation. Large aromatic linkers that are stacked due to the layering of 2D sheets or their connectivity to 1D nodal chains can produce conductive pathways. Ion exchange is also explored both in terms of post-synthetic metal-cation metathesis to acquire thermally and photocatalytically active sites and inorganic anion exchange to tune gas sorption behaviors. This thesis provides insight into the intuitive construction of MOFs with purposeful electronic structure design for targeted applications.en-USAll Rights Reserved.CatalysisConductivityDensity Functional TheoryGas UptakeMetal-Organic FrameworksPhotocatalysisElectronic Thesis or Dissertation