Brozek, CarlMarshall, Checkers2023-07-062023-07-06https://hdl.handle.net/1794/28498Metal-organic framework nanoparticles exhibit both high internal surface area and good colloidal stability in a variety of solvents including biological media. These materials are sought after for a range of applications, mainly in drug delivery, catalysis, and separation membranes. Considerable effort has been put into controlling the size and shape of MOF crystals to develop materials that, due to small particle size and good colloidal stability, may be solution-processable. In this thesis, a simple model to help predict size trends in MOF nanoparticle syntheses is developed, then the model is applied both to well-known and novel MOF nanoparticle systems. In Chapter 2, I first present a simple equilibrium model to further our understanding of how to control MOF nanoparticle size. MOF nanoparticles can be synthesized via several top-down and bottom-up approaches. One of the most prevalent bottom-up methods is to use “modulators,” molecules added to the growth media to change the reaction conditions and therefore the crystals’ growth. This chapter encompasses a literature-based perspective on how the presence and identity of a modulator will impact the final size of a MOF nanoparticle and introduces the “Seesaw model" to explain these effects. In Chapter 3, I then apply this model to the well-known nanoMOF systems Zn(mIm)2 (ZIF-8) and Cu3BTC2 (HKUST-1). We show that, by using a mixture of a conjugate acid/base pair, that both modulator equivalents and proton activity play a role in determining final particle size. In Chapter 4, I first develop the synthesis for a novel nanoMOF system, a family of metal-triazolate MOFs, then explore the MOF Fe(1,2,3-triazolate)2 in more depth for its size-dependent optical and electronic properties. Finally, in Chapter 5, the effects of ion identity, solvent identity, particle size, and film thickness on the redox activity of Fe(TA)2 thin films is studied in depth. This dissertation contains both published and unpublished co-authored material.en-USAll Rights Reserved.metal-organic frameworkmodulatorMOFnanoparticletriazolateElectronic Thesis or Dissertation