Synthesis of self-assembly systems with multiple hydrogen bonding interactions

Supramolecular chemistry and the development of “supramolecular polymers” are of direct relevance to materials science. Defined as “chemistry beyond the molecule, the chemistry of tailor-shaped intermolecular interactions”, supramolecular chemistry is concerned with preparing assemblies of molecules using a combination of secondary chemical interactions rather than covalent bonding. The comparatively simple molecules used in these assemblies are driven to spontaneously self-assemble, and then hold together, via such non-covalent interactions as hydrogen bonds, metal coordination sites and Van der Waals forces. In order to assess whether the functionalization of cytosine with longer alkyl chains affects its properties, 1-methyl cytosine was synthesised as a ureidopyrimidinone (UPy) mimic for incorporation into arrays. The synthesis of further compounds functionalized at N-1 of the cytosine motif has been achieved and is fully described. In order to investigate the strength of the AADD array formation, a 5-fluoromethyl cytosine motif has been studied. Following previous work, the use of quadruple hydrogen bonded units has been investigated and UPy and cytosine units incorporating OH and NH2 terminated polymers have been studied. Subsequently, the synthesis of energetic and non-energetic supramolecular polymers has been achieved. In order to investigate the potentially different physical properties of the telechelic diamine polymers other polymers were synthesized containing a double urea unit. With the purpose of synthesizing an energetic H-bonded polymer the functionalization at N-1 position on cytosine unit with a dioxolane moiety has been examined. Furthermore, a new strategy to difunctionalised cytosine molecules has been explored with the synthesis of and an amino acid derivative. In addition, further investigations into the functionalization at the N-1 position on cytosine via click chemistries have been studied for the adjustment of polymer properties and to synthesize a bifunctional system possessing units at each end. In order to establish functional applications of our materials, large scale syntheses of mono urea polymers have been obtained and properties of the materials fully examined