Metal–organic frameworks (MOFs) are crystalline, porous solids constructed from organic linkers and inorganic nodes that are promising for applications in chemical separations, gas storage, and catalysis, among many others. In particular, MOFs are ideal for greenhouse gas capture applications due to their highly tunable pores, which allow for maximizing uptake and selectivity of target adsorbates. However, a major roadblock to the widespread implementation of MOFs, including highly tunable and hydrolytically stable Zr- and Hf-based frameworks, is their benchtop-scalable synthesis, as MOFs are typically prepared under highly dilute (≤0.01 M) solvothermal conditions. This necessitates the use of liters of organic solvent to prepare only a few grams of MOF. In this thesis, we demonstrate that Zr- and Hf-based frameworks (eight examples) can self-assemble at much higher reaction concentrations than are typically utilized, up to 1.00 M in many cases. Combining stoichiometric amounts of Zr or Hf precursors with organic linkers at high concentrations yields highly crystalline and porous MOFs, as confirmed by powder X-ray diffraction (PXRD) and 77 K N2 surface area measurements. Furthermore, the use of well-defined pivalate-capped cluster precursors avoids the formation of ordered defects and impurities that arise from standard metal chloride salts. These clusters also introduce pivalate defects that increase the exterior hydrophobicity of several MOFs, as confirmed by water contact angle measurements. Overall, our findings challenge the standard assumption that MOFs must be prepared under highly dilute solvothermal conditions for optimal results, paving the way for their scalable and user-friendly synthesis in the laboratory. Finally, this thesis presents that the capture of hydrofluorocarbon greenhouse gases (HFCs) in MOFs can be enhanced via halogen-bonding interactions. HFCs are highly potent greenhouse gases with high global warming potentials (GWPs), and in particular, CHF3 (GWP of 11,700 CO2 equivalents) is unavoidably produced and emitted from the production of fluoropolymers. Evaluating CHF3 adsorption in an isoreticular series of Zr-based frameworks that varied in linker length and incorporation of large, polarizable halogens, demonstrates that the presence of halogen bond donors alongside decreased pore size enhance the binding strength of CHF3 in these materials. Furthermore, a bromofumarate based MOF displaying the strongest binding strength, highest CHF3 uptake at low pressures (<100 mbar), and high CHF3/N2 selectivity was able simulate a CHF3/N2 separation using dynamic breakthrough measurements. More broadly, we provide a new strategy for improving HFC capture performance in porous material-based greenhouse gas capture technologies.