Synthesis and characterization of mixed valent molecules which contain two or more metals in different oxidation states is a rich field of chemistry informing fundamental electronic structure and electron transfer theories. Traditionally these studies are concerned with the direct electronic interaction between metals, but recent work on redox non-innocent ligands has shown that forms of “metal-organic” mixed valency are prevalent but understudied. Using a redox non-innocent ligand as a bridging ligand for a mixed valent system allows investigation of this metal-organic delocalization in the context of the metal-metal interactions. In chapter two the effect of a trinuclear mixed valent system with a delocalized bridging ligand is investigated by permuting the c coordination chemistry of one of the metals and observation that this had little to no effect on mixed valent properties owing to the strong ligand based nature of the delocalization. In chapter three the effect of metal ionic radius and the consequent change in coordination sphere size is investigated for how it affects the bridging ligand geometry. Because molecular geometry is intimately connected to electronic states for mixed valent compounds, this consequently does influence the mixed valent properties of complexes, as seen through increase in NIR charge transfer intensity when small metals that enforce more rigidity are employed.

Creator

• Carter, Cole

DOI

• https://doi.org/10.21985/n2-wt41-a735

Subject

• Inorganic chemistry

Language

• en

Alternate Identifier

• etdadmin_upload_945235
• http://dissertations.umi.com/northwestern:16349

Date created

• 2022-01-01

Resource type

• Dissertation

Rights statement

• In Copyright