Nano-sized molecular-based platforms provide a promising approach to materials which can be used in optoelectronics, switchable redox-driven devices, and dye-sensitized solar cells (DSSC), as well as other technological applications. Poly(ferrocene)-containing compounds with accessible mixed-valence properties at low potentials and broad absorption spectra in the UV-vis-NIR region represent an important class of organometallics which have potential for use in light-harvesting, photocatalysis, and molecular electronics. Target compounds were prepared using previously developed procedures, and characterized using UV-vis-NIR, MCD, and NMR methods. A variety of solvents and electrolytes were used to investigate the redox properties of these poly(ferrocene)-containing porphyrins and tetraazaporphyrins analogues in order to determine their influence on long-range metal-metal coupling. The spectroscopic signatures of the redox-active species were investigated using spectroelectrochemical methods which were well correlated with Density Functional Theory calculations. The mixed valence properties and electronic communication observed in obtained compounds relate to those desired in molecular electronics applications and for use in DSSC's.
University of Minnesota M.S. thesis. August 2013. Major: Chemistry. Advisor: Dr. Victor Nemykin. 1 computer file (PDF); viii, 107 pages.
Synthesis and characterization of ferrocenyl-containing porphyrins and tetraazaporphyrins.
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