Spin-orbit coupling (SOC) is a powerful phenomenon that dictates the functional properties of transition metal complexes essential for information processing, catalysis, and magnetism. Though it is relegated to lower energy scales within the orbital description of first-row transition metal complexes, SOC impacts crucial aspects of electronic structure such as promoting spin-forbidden processes. Therefore, developing approaches to modulate SOC in first-row metal complexes would propel our fundamental understanding of electronic structure and allow tailoring of metal complexes to the aforementioned applications. An attractive platform to probe the nature of SOC relies on using heterobimetallic complexes where we can systematically alter specific parameters through synthetic design. In this approach, heavy main group metals, such as tin, act as ligands to first-row transition metals as an external source of SOC. This splits the key components of SOC onto two different metals which each can be independently varied and interrogated. We hypothesize this metal-metal bond covalency directly affects the transferal of SOC between the two atoms. In this dissertation, I design and explore systems to test how metal-ligand covalency influences SOC through magnetic anisotropy. Chapter 1 will discuss the interplay of ligand field and SOC contributions towards magnetic anisotropy through a review of the literature, and how I approached assessing the influence of covalency on magnetic anisotropy using heavy group 14 metal donors. Chapter 2 explores how subtle control over the local coordination environment influences magnetic anisotropy allowing us to tailor first-row transition metal complexes towards two different applications, molecular magnetism and quantum information processing. Chapter 3 reports a study highlighting the importance of spin-orbital overlap with ligand donor orbitals in ionic versus covalently bound heavy donor atoms. Chapter 4 outlines an approach to studying the influence of metal-metal bond covalency using ligand field theory in complexes with high-spin ground states. In Chapter 5, I spectroscopically probe covalency and periodic trends in a series of high-spin tin-transition metal complexes. Using the aggregate experimental data, I investigate how these periodic trends influence SOC transfer from tin using a molecular orbital approach.

Creator

• Coste, Scott Christopher

DOI

• https://doi.org/10.21985/n2-00rd-0n98

Subject

• Inorganic chemistry
• Physical chemistry

Language

• en

Alternate Identifier

• etdadmin_upload_685992
• http://dissertations.umi.com/northwestern:14821

Date created

• 2019-01-01

Resource type

• Dissertation

Rights statement

• In Copyright