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Title: Self-assembly and gelation behaviour of pyridyl urea complexes
Author: Byrne, Peter
ISNI:       0000 0004 2676 9256
Awarding Body: Durham University
Current Institution: Durham University
Date of Award: 2009
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Bis(3-pyridyl)ureas with ethylene, propylene, butylene, phenylene and napthy- lene spacer groups were synthesised by the reaction of 3-isocyanato-pyridine, pre- pared in situ from nicotinoyl azide, with the appropriate diamine. Each ligand was crystallised and their structures were solved using X-ray crystallography. The urea groups of the napthylene-spaced ligand adopt a bifurcated hydrogen-bonding mode, thereby forming an α-tape whereas in the the propylene-, butylene- and phenylene- spaced ligands, every other bifurcated interaction is replaced with a NH···Ourea and a NH···Npyridyl , caused by the presence of a single competing intramolecular CH···Ourea set-up by the electron-withdrawing pyridyl nitrogen. With the ethylene-spaced urea, the bifurcated hydrogen-bonding motif is absent. These differences in the intermolec- ular bonding may be only be due to the packing requirements of the spacer group: as these interactions become stronger, either by greater van der Waals attraction in a longer oliomethylene chain or the greater π-π stacking interactions of the napthy- lene ring, adjacent urea groups become closer and bind preferentially to form the bifurcated interaction. The bis(3-pyridyl)ureas were subsequently tested for their ability to form gels, and in some cases, crystallised in the presence of selected silver(I) salts. Compound 2.1 formed five pseudo-polymorphs of a Borromean-type structure upon slow crys- tallisation in various solvent mixtures with silver(I) nitrate. Within each struc- ture, there are layers made up of paired Borromean weaves and the mechanism by which these layers stack, though unclear, must ultimately be driven by the inter- actions of the solvent molecules incorporated into the structures. When the coun- teranion in the crystallisation was replaced by either acetate, tetrafluoroborate or hexafluorophosphate, several coordination polymers were synthesised but the Bor- romean structure was not reproduced. A similar dependency on counteranion was observed with N,N''-pentylene-1,5-diylbis(N'-pyridin-3-ylurea) which was similarly crystallised with silver(I) nitrate, acetate and tetrafluoroborate. In the presence of the latter, a quintuple helix formed. Several bis(3-pyridylureas) with ethylene, pyridine, methylenebisphenylene and cyclohexylene spacer groups were shown to form gels and crystals in the presence of silver(I) nitrate. Two macrocyclic structures were grown from gel states which may be further indication as to how the same molecules aggregate in the gel fibres with silver(I) nitrate promoting aggregation of the molecules along one direction.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available