Synthesis and characterization of new classes of polyamine and polyamide anion receptors

The design, synthesis and characterization of polyaza-, polyamido-, and polythioamido-macrocycles were undertaken in this research. This project consisted of several sub-projects, all involving macrocyclic ligands, with a primary goal of achieving selective anion recognition.; In the initial phase of this project, a new design strategy was probed for achieving functionalized polyaza macrocycles (Chapter 7). As the project developed, focus was broadened to include amide- and thioamide-based receptors, which contain pyridine or thiophene spacers as well as at least one amine functionality. The influence of macrocyclic size with respect to anion binding was investigated by the synthesis of 1 x 1 (one spacer and one linker) and 2 x 2 (two spacers and two linkers) condensates of these mixed amine/amide macrocycles.; The 1 x 1 condensate, (Chapter 4), consists of a 14-membered macrocyclic ring whereas the 2 x 2 condensate, (Chapter 5), consists of a 24-membered macrocyclic ring. Amide- and thioamide-based 1 x 1 condensates which contain a propylene linker were shown to have a low binding affinity for anions. A 17-membered 1 x 1 condensate with a thiophene spacer and piperazine linker was also synthesized and showed no anion binding.; Chapter 5 contains amide- and thioamide-based and quaternary 2 x 2 condensate receptors containing a thiophene spacer, which contain an ethylene linker, were shown to have a fairly low binding affinity for anions. Although the binding affinity for anions is fairly low with the thiophene 2 x 2 condensates, a trend is evident with binding affinities increasing from the amide to thioamide to quaternized 2 x 2 macrocycles.; There is a growing interest in our group in utilizing these types of macrocycles to study the formation of metal complexes for potential catalytic applications. In Chapter 6 metal complexes with copper have been made with the pyridine amide 1 x 1 condensate and its analog the pyridine amide 2 x 2 condensate. The 1 x 1 condensate forms a monomeric complex whereas the 2 x 2 condensate forms a dimeric complex. A pyridine amide 2 x 2 condensate with pendent amine arms has also been shown to form a dimeric copper complex. These initial studies could potentially lead to further investigations into catalytic chemistry. X-ray crystal structures of all of the 1 x 1 condensates, thiophene 2 x 2 condensates, and metal complexes have been solved and included in this thesis.