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Title: Calix(4)arene, resorcarene and triaza-adamantane receptors : synthesis, characterisation and cation binding properties
Author: Nwogu, Nwanyinnaya Akuagwu
ISNI:       0000 0004 2673 2226
Awarding Body: University of Surrey
Current Institution: University of Surrey
Date of Award: 2009
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Following an overview of Supramolecular Chemistry, the main focus of this thesis was to assess by different methods (1H NMR, X ray crystallography, conductance and potentiometric measurements and titration calorimetry) the interaction of ions with various receptors (phenylketone calix[4]arene L1, diethylamine resorc[4]arene L3, diethyl thiophosphate resorc[4]arene L4, and 7-nitro-1,3,5-triaza adamantine L5) in non aqueous solvents. Solubility measurements of these ligands were carried out in various organic solvents at 298.15 K. These data were used to calculate the standard Gibbs energies of solution SG, and transfer tG, of these ligands from a reference solvent to another. 1H NMR investigations showed that L1 interacts with alkali, alkaline earth, transition and heavy metal cations in deuterated acetonitrile at 298 K while in the same solvent, L3 behaves as a ditopic ligand. In moving to deuterated dimethylsulfoxide, L3 interacts only with silver (I) and mercury (II) metal cations showing once again the effect of the medium on the complexation process. Silver and mercury complexes were also found for L4 in deuterated acetonitrile. In this solvent L5 showed interaction with the heavy metal cations only and therefore this proves to be an interesting moiety to be incorporated as pendant arm in calixarene, calixpyrrole and resorcarene receptors. Conductance measurements were performed with the aim of determining the composition of the complexes and these are reported. The selectivity of the ligands for one ion relative to another was quantitatively assessed from the thermodynamics of ionic complexation involving these receptors using acetonitrile as the solvent. X ray studies were also performed to characterize the resorcarene receptors and the mercury (II) and silver (I) adamantane complexes. Final conclusions are given.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available