Date of Award
Doctor of Philosophy (PhD)
Eric J. Schelter
Patrick J. Walsh
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.
Robinson, Jerome Ronald, "F-Element Binolate Complexes: Control of Secondary Structure for Applications in Redox Chemistry, Complex Design, and Asymmetric Catalysis" (2014). Publicly Accessible Penn Dissertations. 1421.