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Paramagnetic Resonance Spectroscopy of Cobalt(II) Tripodal Amines
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Paramagnetic Resonance Spectroscopy of Cobalt(II) Tripodal Amines
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Dissertation
Paramagnetic Resonance Spectroscopy of Cobalt(II) Tripodal Amines
2024
Overview
This dissertation investigates the magnetic properties of several series of structurally-related molecules. Distinctions in their magnetic properties are studied using multiple spectroscopic techniques, coupled with structural determinations and theoretical calculations.In Chapter 2, a tripodal ligand tris-(2-pyridylmethyl)amine (tpa) and the corresponding series of air-sensitive, high-spin Co(II) complexes are developed by altering one monodentate ligand. Variable temperature paramagnetic relaxation measurements using NMR and structural parameter determination by SC-XRD are presented. Deviations in electronic transitions are studied using EPR and UV-vis. DFT calculations are carried out using ORCA to extensively explore and correlate the data between multiple techniques, enabling a comprehensive analysis of molecular motions.Chapter 3 explores unique examples of a six-coordinate Co(II) complex crystallized in four distinct packing motifs. Using SC-XRD and EPR, the influence of the non-covalent interactions (T-stacking) and the spatial arrangement of a chemical moiety within a molecule are studied on the spin-switch behavior. Multiple solvent VT-NMR, Evan’s NMR, UV-vis, and MS were utilized to substantiate the analyses.Chapter 4 investigates structural dynamics in two novel pentacoordinate Co(II) complexes based on the tripodal ligand tris((1-benzyl-4-triazolyl)methyl)amine (tbta). Utilizing UV-vis, EPR, and VT-NMR, these complexes, featuring an anionic monodentate ligand and tbta were comprehensively investigated in solution.Chapter 5 presents the synthesis and detailed crystallographic structural examination of a unique five-coordinated Co(II) complex. The complex showcases a first-of-its-kind combination of the tripodal ligand tbta and the neutral ligand imidazole.
Publisher
ProQuest Dissertations & Theses
Subject
ISBN
9798383217917
