Associates of 3',5'-O-TBDMS protected derivatives of the 2'-deoxy forms of the nucleosides adenosine, 6-N-methyl-adenosine and thymidine (henceforward simply addressed by their parents' names) and further model systems in dichloromethane and Freon (CDClF2/CDF3) solutions are studied at low temperatures by 1H NMR and FT-IR spectroscopy. N⋯N distances in hydrogen bonds are estimated from chemical shifts of protons in hydrogen bonds employing geometric and spectroscopic hydrogen bond correlations. These distances are in turn employed to derive N–H stretching frequencies from IR spectroscopic hydrogen bond correlations which may be compared to corresponding experimental results. Three isomeric hydrogen bonded dimers of thymidine are characterized in Freon solution at 120 K. Binary associates of thymidine and a series of pyridines are studied; estimated N⋯N distances in the range of 3.08 to 2.85 Å are qualitatively correlated to shifts of N–H stretching bands where in all cases considerable contributions are found in the spectral region below 3000 cm-1. For adenosine, three isomeric binary associates with 4-nitrophenol are found allowing for an assessment of site-specific acceptor capabilities. In associates of thymidine and adenosine, Watson-Crick and Hoogsteen type 1:1 associates (estimated N⋯N distances of 2.85 and 2.90 Å) as well as 2:1 associates bearing only marginally longer H-bonds could be characterized. Two 1:1 associates between thymidine and 6-N-methyl-adenosine are described that are exclusively bonded via N–H⋯N bridges of about 2.97 and 3.08 Å for Watson-Crick and Hoogsteen sites, respectively, which leads to the conclusion that cooperative effects among coupled N–H⋯O and N–H⋯N hydrogen bonds in A-T base pairs are significant as formation of the N–H⋯O bond induces a contraction of around 0.15 Å in the neighboring N–H⋯N bond.
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