Date of Award
Spring 2026
Abstract
Iron plays an important role in biological processes, while also being implicated in a number of disease processes. Iron chelating ligands incorporating 8-hydroxyquinoline are of interest due to the wide range of potential therapeutic uses. Density Functional Theory (DFT) can be used to design and analyze novel iron chelators. Because DFT methods are generally optimized for main group elements, applying these methods to transition metal complexes can be challenging. To assess the accuracy of DFT computations performed at different levels of theory, the results of geometry optimizations were compared to the X-ray crystallographic structure for Cox200, a previously characterized hexadentate, tripodal ligand based on 8-hydroxyquinoline. Because of the inconclusive results of the Cox200 computations, a previously published computational study of 8-hydroxyquinoline ligands with high spin iron(III) was chosen as a starting point for further computational work. Initially, we replicated the prior computational results using the bidentate ligand 8-hydroxyquinoline-7-methylcarboxylate (OHQ) to form the hexadentate complex Fe(OHQ)3. We undertook an expanded computational approach to assess which of the mer, fac, or salicylate bonding modes represent the most likely structure for Fe(OHQ)3. Novel linear hexadentate ligands were then designed based on the Cox200 and Fe(OHQ)3 studies and best practices from the computational literature. An iterative design process resulted in 5 novel ligands predicted to form hexadentate complexes with high spin iron(III). The resulting optimized structures and reaction energies were analyzed for each complex. There is a bright outlook for future application of this work to assess and refine the design of novel ligands.
Document Type
Master's Thesis
First Advisor
Roy P Planalp
Second Advisor
Christopher F Bauer
Third Advisor
Carmela Amato-Wierda
Department or Program
Chemistry
Degree Name
Master of Science
Recommended Citation
Adams, Ariel, "DENSITY FUNCTIONAL THEORY APPROACHES FOR IRON CHELATORS" (2026). Master's Theses and Capstones. 2079.
https://scholars.unh.edu/thesis/2079