Physical Sciences and Mathematics Commons^™

Understanding The Effects Of Ligand Environment On Important Properties Of Redox-Active Europium Using Computational Chemistry And T1-Weighted Magnetic Resonance Imaging, Brooke Anne Corbin

Wayne State University Dissertations

This thesis is a collection of seven chapters that describes a combination of literature research and experimental analyses into the study of inorganic complexes, with an emphasis on the photophysics and coordination of redox-active europium. The first chapter summarizes the key features of each chapter. The second and third chapters are detailed overviews, including historical context, current studies, and future goals of imaging science, with an emphasis on inorganic complexes. The fourth chapter describes the design of a screening procedure to study new ligand environments for redox-active europium using magnetic resonance imaging and a proof-of-concept experiment. The fifth chapter is …

The Effects Of Coordination Environment On The Spectroscopic And Electrochemical Properties Of Divalent Lanthanides, Tyler C. Jenks

Wayne State University Dissertations

The research projects in this dissertation pertain to the properties of molecular divalent lanthanide complexes with a focus on luminescence properties in solution. Most available research in lanthanide chemistry focuses on either the trivalent oxidation state or the divalent oxidation state in solid inorganic host matrices. The results described herein contribute to the body of knowledge regarding the effects of coordination environment on the spectroscopic and electrochemical properties of divalent lanthanides in solvated molecular complexes.

The divalent-europium-containing complex Eu(II)23 was evaluated as a visible-light-excited photoredox precatalyst. Stoichiometric and catalytic carbon–carbon bond forming reactions of Eu(II)23 with benzyl chloride in the …

Europium(Ii)-Containing Complexes For Responsive Magnetic Resonance Imaging, Levi Alexander Ekanger

Wayne State University Dissertations

The research projects described in this dissertation are focused on studying the oxidation of EuII-containing complexes within the context of responsive MRI. Prior to this research, EuII had not been explored within the context of oxidation-responsive MRI nor had the use of this ion been reported in vivo. The results of these studies enable predictions about the oxidation-responsive behavior of EuII-containing complexes in vitro and in vivo.

The EuII-containing cryptate 1.33 was used to evaluate EuII-based positive contrast enhancement after intravenous, intraperitoneal, and subcutaneous injections. The transitory behavior of the positive contrast enhancement correlated with reported levels of oxygenation and …

Lanthanide-Based Precatalysts For Carbon-Carbon Bond-Forming Reactions In Aqueous Media, Derek James Averill

Wayne State University Dissertations

The formation of carbon-carbon bonds is of great interest to synthetic chemists because these bonds make up the majority of biologically active compounds. The Mukaiyama aldol reaction is a Lewis-acid-catalyzed carbon-carbon bond-forming reaction that has the ability to produce optically active β-hydroxy carbonyls which can be found in many pharmaceuticals and natural products. Because of precatalyst instability towards hydrolysis, anhydrous solvents are commonly used. Recent efforts have focused on water-tolerant versions of enantioselective Mukaiyama aldol reactions because of the financial and environmental benefits of using aqueous media. Consequently, the Lewis-acidic and water-tolerant features of Ln³⁺ ions have aroused great …

Energy Transfer In A Discrete, Soluble Heterobimetallic Complex Containing Tb3+ And Eu3+, Nikhil Kumar Barua

Wayne State University Theses

A discrete, heterobimetallic Tb3+-Eu3+ -containing complex has been synthesized, and energy transfer was observed in the complex without using an antenna. This result represents a new way of observing lanthanide emission using lanthanide excitation in discrete, soluble complex. The occurrence of energy transfer in the mixed heterobimetallic Tb3+-Eu3+ complex was characterized using steady state luminescence spectroscopy and luminescence-decay studies. These findings are likely to be useful for fundamental mechanistic studies of energy transfer in lanthanide-containing systems.