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| - Hydrogen Bonding and π-Stacking Interactions as OrganizingElements in Lariat Ethers Containing Nucleotide Bases
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| - Two new bibracchial lariat ethers have been prepared asflexible model systems for nucleotideH-bonding and π-stacking interactions. In both compounds,nucleotide bases terminate side armsattached at the nitrogen atoms of a diaza-18-crown-6 macroring.Each side arm is terminated byone or more nucleotide bases. The unsymmetrical structure isade-CH2CH2<N18N>CH2CH2CH2-thy-CH2CH2-ade (A−O−T−A). Thesymmetrical compound isade-CH2CH2-thy-CH2CH2CH2<N18N>CH2CH2CH2-thy-CH2CH2-ade(A−T−O−T−A). NMR studies show that thethy−adeside arm organizes by π-stacking in both A−O−T−A andA−T−O−T−A. Both compounds exhibithydrogen bonding between the stacked base pair and the oppositeadenine. A−O−T−A exhibits astronger interaction resulting from the enforced interplay ofnoncovalent forces, as evidenced byone- and two-dimensional NMR experiments. This compound alsopresented the opportunity todetect and examine single hydrogen-bonded interactions between twoadenine bases. The effectsof conformational rigidity, side arm orientation, metal ioncomplexation, and variations in solventwere assessed for both compounds. The results presented hereindicate that an increase in themedium's dielectric constant or complexation of metal cations appearto modulate the interplaybetween hydrogen bonding and stacking interactions.
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