Date of Award

2014

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Graduate Group

Chemistry

First Advisor

Eric J. Schelter

Second Advisor

Patrick J. Walsh

Abstract

Rare earth elements (REs; Sc, Y, La - Lu) are critical components to many current applications and technologies making the synthesis of molecular compounds with specific and tunable properties highly desirable. However, control of the coordination environment of REs can be challenging, due to the ionic nature of the metal-ligand bonds. Our studies have focused on the introduction of non-covalent interactions in the secondary coordination sphere of f-element BINOLate complexes, which enabled controlled f-element coordination environments in heterobimetallic and hydrogen-bonded frameworks. Reactivity and properties were tunable by interactions in the secondary coordination sphere, and had immediate applications to redox chemistry, coordination chemistry and asymmetric catalysis. Detailed spectroscopic and mechanistic studies were undertaken to understand the role of these interactions, and provide guiding design principles for future systems and applications.

Files over 3MB may be slow to open. For best results, right-click and select "save as..."

Share

COinS