Date of Award

12-2016

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Dr. Ekkehard Sinn

Second Advisor

Dr. Donald Schreiber

Third Advisor

Dr. Yirong Mo

Fourth Advisor

Dr. James Springstead

Keywords

Complex, copper, phthalocyanine, catalysis, naoanchoring, ligands

Abstract

Design and synthesis of ligands that can complex two different metals at two different sites are constructed. Larger ligand binding structures are attached to synthesized imidazoles. One imidazole nitrogen participates in binding the larger ligand to a first metal and the second imidazolate anion post-ionization acts as a bridge to bond to a second different metal species. The first metal bound to the larger ligand structure is a copper metal. Different transition metals, namely iron or zinc, are used as the second metal. The resulting binuclear complex acts as a biological mimic for the enzyme active site where the imidazole bridging action to metals is analogous to Cu-Zn bovine erythrocyte superoxide dismutase enzyme-substrate binding.

Carboxylated copper phthalocyanine building blocks for hydrogen storage and CO2 sequestering are non-toxic thermodynamically stable materials for which there have been reported exceptionally high dielectric constants making them useful for electric components and possibly photovoltaic systems. Synthesis of several oligomers, especially the monomer and tetramer of the copper phthalocyanines is performed in a one pot synthetic route. Development of analytical methods using electro-spray ionization mass spectrometry to characterize the final products is carried out. Size exclusion methods for separation and silica gel columns for purification are utilized. Isolation of the tetramer in sufficient yield is attempted and determined to not be possible in bulk yield due to monomeric clusters formed upon synthesis. Based on this finding, applying it as a molecular panel building block for construction of metal organic frameworks having storage capabilities for molecules such as hydrogen and carbon dioxide is not possible as sought.

Investigation into the design of pyrrole copper oxidase catalysts and attempted synthesis of complexes is achieved. Crystals of the complexes having water associated with open copper sites along with other solvents are obtained. These further the understanding of the idealized structure of such complexes for both in vitro and in vivo investigations for their applications in the medical field as well as in industrial catalysis.

Access Setting

Dissertation-Campus Only

Restricted to Campus until

12-15-2026

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