Tetrathiafulvalene Schiff-base ligands and anion receptors

Abstract

Over the last decade, the classic organic donor tetrathiafulvalene (TTF) has emerged as an important functionality in supramolecular systems and complex ligand chemistry. Due to synthetic advances, TTF is no longer a moiety strictly limited to the area of charge transfer salts in material science. In fact, many complex systems incorporating the electron rich donor system are known. More can be imagined. This doctoral dissertation describes the author's journey in designing, synthesizing, and studying various compounds in which the TTF moiety serves a practical purpose, oftentimes giving known molecules new functions. The reported findings have led to a greater understanding of anion binding effects on TTF-containing anion receptors, the use of transition metals to pre-organize [pi]-faces for through-space donor-acceptor interactions, and the introduction of actinide species to tetrathiafulvalene ligands. The first Chapter provides a brief introduction and a short history of TTF chemistry. It also provides an overview describing the fundamental properties of TTF compounds, including TTF dimeric behavior and redox properties. Chapter 2, as the major focus of this dissertation, details the use of a flexible TTF-modified macrocyclic ligand, which upon metallation can effectively preorganize two TTF units to interact when oxidized. Specifically, a new way to stabilize the through-space mixed-valence TTF dimer, in which a transition metal can affect the degree of interaction between the two TTF units, is described. The mixed-valence TTF species in question could see use as components in molecular machines and could play an important role as molecular organic conductors, and discussions along these lines are included in this chapter. These mixed valence complexes were investigated by spectroscopic (¹H-NMR, UV-Vis NIR titrations, and EPR analysis) and X-ray single crystallographic analyses involving both the neutral and oxidized products. Chapter 3 introduces the synthesis, characterization, and electrochemistry of the first TTF-ligand to form a complex with an actinide cation. Chapter 4 details the synthesis, binding studies and X-ray single crystallographic analyses of a TTF-based electrochemical sensor for dihydrogen phosphate anion detection. Experimental procedures and characterization data are reported in Chapter 5.