Studies directed toward the fabrication of synthetic, cation-conducting channels

Date of Award




Degree Name

Doctor of Philosophy (Ph.D.)



First Committee Member

George W. Gokel, Committee Chair


4,13-diaza-18-crown-6 derivatives having acidic protons in sidearms such as: $N,N\sp\prime$-$bis$(2-hydroxyethyl)-4,13-diaza-18-crown-6, $N,N\sp\prime$-$bis$(2-hydroxylethyl)-4,13-diaza-18-crown-6$\cdot$Nal complex, $N,N\sp\prime$-$bis$(2-hydroxybenzyl)-4,13-diaza-18-crown-6, $N,N\sp\prime$-$bis$(2-aminoethyl)-4,13-diaza-18-crown-6, $N,N\sp\prime$-$bis$(2-aminobenzyl)-4,13-diaza-18-crown-6, $N,N\sp\prime$-$bis$(carbamoylmethyl)-4,13-diaza-18-crown-6, and $N,N\sp\prime$-$bis$- (N$\sp{\prime\prime}$-(acetyl)glycine) -4,13-diaza-18-crown-6 were prepared and intramolecular hydrogen bonding was studied by IR spectra, NMR spectra, X-ray crystallographic structure determination, and thermodynamic measurements.In order to develop a model of molecular cation conducting channels, we undertook the preparation of a cyclophane held together by intermolecular hydrogen bonding. The monomers prepared for this study were $N,N\sp\prime$-$bis$ (9-(3-propyl)adeninyl) -4,13-diaza-18-crown-6 and $N,N\sp\prime$-$bis$ (1-(3-propyl)thyminyl) -4,13-diaza-18-crown-6. The monomers self-associated into a cyclophane, held together by specific interactions of DNA-type between adenine and thymine. The extent of association increased when 1, 12-dodecanediammonium dication was added. Additional modes for molecular channel compounds have also been developed. These are based on both the rigid and the self-assembly concepts. The rigid channel forms consist of two macroring held face-to-face by diacetylene chains or by polymethylene chains. The self-assembling cation channel compounds are based on tris(macrocyclic) system. In a preliminary $\sp{23}$Na-NMR study of cation complexation, it was found that the Na$\sp+$ ion jumps from the bottom to the top macroring in the tetraacetylene cyclic dimer compound.


Chemistry, Organic

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