Hydrogen bonded cavity and polymeric nanotubular assemblies from small bicyclic monomers /

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.

Grantor dc:publisher

Institutional Repository of Vilnius University

Year dc:date

2016

Author dc:creator

• Anderson, Dovilė,

Contributors dc:contributor

• Butkus, Eugenijus
• Orentas, Edvinas

• tubular polymers ; hydrogen bonding ; self-assembled capsule ; tautoleptic aggregation

Statement dc:rights

• info:eu-repo/semantics/openAccess

Language dc:language

eng

Repository record dc:identifier

https://repository.vu.lt/VU:ELABAETD16990407&prefLang=en_US

OAI identifier oai:identifier

oai:vu.lt:elaba:16990407