Assembly and recognition processes are very common natural phenomena, and are primarily controlled by numerous selective non-covalent interactions. The self-assembly of synthetic complementary sequences solely through hydrogen bond interactions is an important potential approach to the development of artificial double helices and hydrogen-bonded supramolecular polymers. This thesis describes the design, synthesis, and characterization of a series of alternating and contiguous (self-)complementary hydrogen-bonded duplexes based on a 1,4-thiazine-1,1-dioxide (donor, D) and pyridine (acceptor, A) motif.;It was proven by experiment that there was unfavourable interference caused by intramolecular hydrogen bond interaction between the neighbouring donors and acceptors in the pyridine-based alternating sequences. Modification by addition of methyl substituents increased the interplanar torsion angle and therefore efficiently prohibited intramolecular hydrogen bonding.;A comparison of the results obtained from duplex formation by the sequences DD·AA and AD indicated that secondary interactions had a strong influence on duplex stability, which supports Jorgensen's hypothesis concerning nucleobase-like systems. Steric effects and the weak electron donating nature of the methyl substituents, attached to DD and AA, were observed as well.;The double helical structures of several duplexes were confirmed by single crystal X-ray crystallography and demonstrated the intended design in the solid state.;A general and practical synthetic method that produces different 1,4-thiazine-1,1-dioxide and pyridine sequences with reliable yields were developed. The formation of hydrogen-bonded duplexes from these sequences was characterized by solution NMR, UV-vis spectroscopy and X-ray crystallography.;Ail these obtained results provide useful guidelines for designing tightly integrated hydrogen-bonded sequences in non-coplanar systems.;Keywords. Hydrogen bonding, Duplexes, Supramolecular chemistry, Secondary interaction, Complementary, Sequence, Double helix.
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