Sudhakaran Pillai, S. (2010) Luminescent materials based on Lanthanide ions. (PhD thesis), Kingston University, .
Abstract
The inclusion of lanthanide (III) (Ln[sup]3+) ions into polymers by “covalent” bonding has applications. Heteroleptic hydrotris(pyrazolyl)borate crotonate and cinnamate complexes were synthesised for reasons that, firstly, knowledge of the polymerisable double bond was helpful in establishing the conditions of any copolymerisation reaction; secondly, the chosen ligands are very good at receiving energy in the UV region; and thirdly, lanthanide complexes might undergo changes in properties, on moving between adjacent lanthanide ions, allowing potentially convenient isolations of pure materials at the monomer production stage, or even at the polymerisation stage. For both complexes, two classes of target complex were identified: the mononuclear (Er-Lu) and dinuclear (La-Ho). Mononuclear forms were identified by MS, [sup]1H NMR and elemental analysis and dinuclear forms were characterised by X-ray crystallography. For heteroleptic hydrotris(pyrazolyl)borate crotonate and cinnamate complexes, the ligands act as antennae for receiving and then transferring energy to metal ions and these complexes were studied in several homogeneous and heterogeneous copolymers as well as in rigid PMMA or polystyrene matrices. Luminescence decay of these complexes depends on the distance between the metal and C-H oscillators so the cinnamate complexes showed better luminescence life-times compared to crotonate complexes. The copolymer system helped to reduce the concentration quenching compared to corresponding metal complex / polymer blend systems. The thermal stabilities of the complex monomers were increased by incorporating them into polymer chains. Europium crotonate and cinnamate complexes in the poly(p-phenylenevinylene) (PPV) precursor blends showed the characteristic emission of europium, and the emission from PPV was quenched by increasing the europium content in the PPV precursor blends.
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