Date of Award


Degree Type


Degree Name



Chemistry and Biochemistry

First Advisor

Loeb, Stephen J.,


Chemistry, Inorganic.




This thesis describes the study of two different pairs of heteroditopic macrocyclic ligands. The main emphasis is placed on the synthesis and characterization of the receptor:substrate complexes. In Chapter 2, the synthesis and chemistry of SOX-5 and SOX-6 are explored. The ligands contain separate thiacrown and crown ether moieties linked by an aromatic spacing unit. The two different coordination sites provide locations for the binding of a soft transition metal (Cu(I)), as well as a hard alkali metal ion (Na$\sp{+}$ or K$\sp{+}$) within the same molecule. The haptoselectivity of the ligands was studied by $\sp1$H NMR and X-ray crystallography, with the attainment of the structures of SOX-5, (CuI(SOX-5)) and (CuI(SOX-6)). The main goal was the cooperative coordination of the sodium salts of AMP, ADP and ATP and the appearance of the $\sp1$H NMR spectra is consistent with coordination of NaAMP and NaADP, but not $\rm Na\sb2ATP$. In Chapter 3, a pair of novel receptors are studied. The metallated macrocyclic hosts, $\rm \lbrack Pd(TOMB$-$\rm P4)(CH\sb3CN)\rbrack\sp{+}$ and $\rm \lbrack Pd(TOMB$-$\rm M4)(CH\sb3CN)\rbrack\sp{+}$, employ simultaneous first- and second-sphere coordination to bind aromatic substrates. This is accomplished by $\sigma$-donation to a palladium centre in conjunction with hydrogen bonding and aromatic stacking interactions. The substrates utilized were p-aminopyridine, m-aminopyridine and the nucleobases, adenine, guanine, cytosine and their derivatives, 9-ethyladenine, 9-ethylguanine, l-methylcytosine. (Abstract shortened by UMI.)Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1996 .M86. Source: Masters Abstracts International, Volume: 37-01, page: 0267. Adviser: Stephen J. Loeb. Thesis (M.Sc.)--University of Windsor (Canada), 1996.