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Keniley, L. K. (2013). Tetrathiafulvalene-Annulated Phenanthroline and Its Complexes with Transition Metals. Retrieved from http://purl.flvc.org/fsu/fd/FSU_migr_etd-7447
Recent interest in designing multifunctional transition metal complexes that incorporate the redox-active tetrathiafulvalene (TTF) molecule stems from the perspective of embedding specific localized properties of transition metal ions into TTF-containing substructures characterized by extended delocalized conduction pathways. This dissertation reports on the synthesis of tetrathiafulvalene, a ubiquitous component of organic conductors, fused directly to 1,10-phenanthroline, one of the most popular ligands in transition metal chemistry. We have devised and implemented a synthetic pathway to this unique ligand, which then was used to obtain complexes with Ru(II) and Fe(II) ions. Chapter 1 of this dissertation provides an introduction to the chemistry of TTF and its metal complexes. Chapter 2 describes the most important methods of characterization employed in this research project. Chapter 3 is devoted to the preparation and properties of the TTF-annulated phenanthroline ligands. Chapter 4 describes a detailed study of a Ru(II) complex of TTF phenanthroline, including its structural, photophysical, and electrochemical properties. [Ru(bpy)2(edt-TTF-phen)](PF6)2 exhibits a unique helical packing of molecules in the crystal structure. In contrast to its TTF-free analogues, this complex contains a TTF-centered highest occupied molecular orbital, and the electrochemical data show that the first two oxidations of the complex are TTF-based. Examination of the photophysical properties revealed that this Ru(II) complex experiences excited-state luminescence quenching via reductive electron transfer from the TTF to the Ru3+ center, which opens up a path for non radiative relaxation to the ground state through the low-lying intra-ligand charge transfer state. We also describe an unusual photoreactivity of this complex that leads to the cleavage of the central C=C bond of the TTF unit in solution. Such reactivity was monitored by the evolution of NMR, UV-visible, emission, and transient absorption spectra. Chapter 5 describes spin-crossover behavior of [Fe(NCS)2(L)2] (L = edt-TTF-phen or hexS2-TTF-phen) and parent Fe(II) complexes. The complex with hexyl substituents is highly soluble and exhibits reversible oxidations centered on the TTF fragments. The observed spin transition was elucidated with variable-temperature Mössbauer and infrared spectroscopies.
Coordination chemistry, Hybrid materials, Intra- and intermolecular energy transfer, Multifunctional materials, Photochemistry and photophysics, Spin-crossover
Date of Defense
June 24, 2013.
Submitted Note
A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy.
Bibliography Note
Includes bibliographical references.
Advisory Committee
Michael Shatruk, Professor Directing Dissertation; James S. Brooks, University Representative; Ken L. Knappenberger, Jr., Committee Member; Albert E. Stiegman, Committee Member.
Publisher
Florida State University
Identifier
FSU_migr_etd-7447
Use and Reproduction
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Keniley, L. K. (2013). Tetrathiafulvalene-Annulated Phenanthroline and Its Complexes with Transition Metals. Retrieved from http://purl.flvc.org/fsu/fd/FSU_migr_etd-7447
