Title Hydrogen bonded cavity and polymeric nanotubular assemblies from small bicyclic monomers /
Translation of Title Ertminės ir polimerinės nanovamzdelinės savitvarkės sistemos, susiformavusios dėl vandenilinių ryšių tarp mažų biciklinių monomerų.
Authors Anderson, Dovilė
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Pages 127
Keywords [eng] tubular polymers ; hydrogen bonding ; self-assembled capsule ; tautoleptic aggregation
Abstract [eng] In this work strategies that allow control of supramolecular outcome of monomers containing bicyclic framework fused with isocytosine and/or ureidopyrimidinone motifs are discussed. The control over aggregation is attained by changing the size of the side chains and by attaching carbamide substituents at the isocytosine motif. Formation of a complex H-bonded decameric capsule assembled from bis-isocytosine monomers in CS2 is presented. The assembly is driven by solvent induced tautomerisation of the isocytosine motif, i.e. heteroleptic aggregation, and simultaneous establishment of 3H- and 2H-bonding modes. The large cavity of the capsule was utilized for C60 inclusion. Enantiomer resolution of 9-benzyl-9-azabicyclo[3.3.1]nonane-2,6-diol was performed. This precursor was utilized in the synthesis of bis-isocytosine monomers, which assemble into polymeric nanotubes. The tubular assemblies are held by orthogonal inter-tetramer H-bonding interface, established after tautoleptic aggregation into tetrameric rings. Bis-ureidopyrimidinone monomers were synthesized and their aggregation in solution investigated. Short organic nanotube composed of eight identical monomers that incorporates isocytosine and ureidopyrimidinone motifs was designed. After isocytosine-ureidopyrimidinone hetero-association via 3H-bonding new inter-tetramer H-bonding interface is created. The octameric tube undergoes extreme structural switch into cyclic tetramer upon inclusion of C60 and C70 guests.
Dissertation Institution Vilniaus universitetas.
Type Doctoral thesis
Language English
Publication date 2016