Williams, James Anthony Gareth (1995) Luminescence behaviour of macrocycle metal complexes. Doctoral thesis, Durham University.
Luminescent complexes of lanthanide ions are of growing interest because the long lifetime of emission allows time-resolved detection procedures to be employed. A key step in the development of such systems lies in the preparation of highly luminescent complexes which display high stability in aqueous solution. A series of ligands based on 1,4,7,10-tetraazacyclododecane have been prepared, in which the nitrogen atoms are appended with coordinating phosphinate or amide groups, or a combination of both. The compounds obtained are octadentate ligands which form water-soluble lanthanide complexes of high stability. Complexes incorporating aryl groups in the pendent arms have been prepared and some display intense metal luminescence following excitation into the organic chromophores. A back energy transfer process occurs in the terbium complexes containing naphthyl or quinohnone groups. Measurements of the luminescence lifetimes in H(_2)O and H(_2)O show diat diere are no metal-bound water molecules in the tetrabenzylphosphinate complexes. Those incorporating one amide and three phosphinate groups display hydration states between 0 and 1. An attempt has been made to correlate this information with that obtained from an analysis of the nuclear magnetic resonance dispersion profiles of related gadolinium complexes. The complexes incorporating secondary amide groups display an additional deactivation pathway for the metal excited state involving energy transfer into N-H bonds. The luminescence behaviour of four macrocyclic tetraamide ligands incorporating naphthyl fluorophores has been studied. These compounds exhibit distinctive changes in luminescence in the presence of quenching (eg. Pb(^2+), Cu(^2+) and Ni(^2+)) and non- quenching ions (eg. Cd(^2+) and Zn(^2+)). This behaviour extends to non-aqueous solution. The protonated tetranaphthyl ligand forms an intramolecular excimer in which the excimer emission displays a sensitive dependence on the polarity of die solvent.
|Item Type:||Thesis (Doctoral)|
|Award:||Doctor of Philosophy|
|Copyright:||Copyright of this thesis is held by the author|
|Deposited On:||24 Oct 2012 15:07|