Physical Sciences and Mathematics Commons^™

Design Of First-Row Transition Metal Bis(Alkoxide) Complexes And Their Reactivity Toward Nitrene And Carbene Transfer, James Bellow

Wayne State University Dissertations

The novel alkoxide ligand [OCtBu2Ph], or [OR], was synthesized in a single step as a lithium salt. It was then reacted with a series of first-row transition metal(II) halides, with widely varying results. Upon reaction with chromium, manganese, iron, or cobalt(II) chloride, dimeric complexes of the form M2(OR)4Li2Cl2 were formed, which displayed rare seesaw geometry at the metal. This unusual geometry was confirmed by various spectroscopic and computational studies. Computational studies also indicate that the steric bulk of the ligand, as well as the inclusion of lithium atoms in the molecules, are what lead to the seesaw geometry. Reaction of …

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 …

Synthesis And Heteroallene Reactivity Of Bis(Aldimino)Pyridine Nickel Complexes In Four Different Oxidation States, Blake Reed

Wayne State University Dissertations

A series of redox non-innocent bis(aldimino)pyridine ligands were synthesized. These were then reacted with nickel(II) salts to form Ni[NNN]X2 complexes. Cyclic voltammograms of these nickel(II) complexes suggest that more reduced states can be achieved. Reduction of these nickel(II) complexes lead to distorted square planar complexes with the halide bent ~20° out of the plane. EPR suggests that spin density is located on the metal as g-values of >2.01 were obtained. This differs from previously reported analogous bis(ketimino)pyridine complexes, which show a ligand-based radical and nickel(II). DFT confirms that as the Npyr-Ni-X angle decreases, spin density on the nickel increases. Because …

New Approaches To Chalcogenide Materials For Thermoelectrics: Lead Telluride-Based Nanostructures And Facile Synthesis Of Tetrahedrite And Doped Derivatives, Derak Justin James

Wayne State University Dissertations

The overall purpose of this work is to address several of the roadblocks to use of thermoelectric materials for generation of electricity, namely inefficient processing of materials and low performance, commonly rated by the figure of merit, ZT=T2/tot. The ZT includes  as the Seebeck coefficient,  as electrical resistivity, T as the average temperature, and tot as total thermal conductivity. tot is the sum of electronic charge carrier (C) and lattice (L) contributions to thermal conductivity. Attempts to increase ZT in the literature to values >1 have focused on decreasing the thermal conductivity via nanostructuring or optimizing the electrical …

Electron Transfer Studies In Langmuir-Blodgett Films Of Metallosurfactants For Current Rectification, Corrosion Mitigation, And Water Oxidation, Sunalee Gonawala Jayasundara Mudiyanselage

Wayne State University Dissertations

The work presented in this dissertation is focused on the design and synthesis of new redox-active amphiphilic architectures to optimize and understand the redox, electronic, and film formation properties for applications in current rectification, corrosion mitigation, and water oxidation. As such, new redox-active, and amphiphilic iron(III), cobalt(III), nickel(II), copper(II), and zinc(II) complexes were synthesized as precursors for Langmuir-Blodgett films used for the aforementioned applications.

For the use in molecular rectification, amphiphilic copper(II) and nickel(II) complexes with [N2O2] ligand environment were synthesized. Homogeneous film formation ability was observed between ~20-25 mN/m pressure, with a film collapse observed at ~35 mN/m for …