TY  - UNPB
UR  - https://discovery.ucl.ac.uk/id/eprint/17980/
PB  - UCL (University College London)
M1  - Doctoral
AV  - none
A1  - Greco, E.
Y1  - 2009/03//
EP  - 249
ID  - discovery17980
TI  - Synthesis of self-assembly systems with multiple hydrogen
bonding interactions
N1  - Authorisation for digitisation not received
N2  - 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.
ER  -