Energy transfer in lanthanide complexes

This thesis details investigations into the photophysical properties of lanthanide ions in a number of different systems. The preparation and characterisation of lanthanide containing surfactant salts of the type Ln(A0T)(_3) (Ln = Tb, Nd, Eu, AOT = bis-(2-ethylhexyl) sulfosuccinate) is described. Small angle neutron scattering experiments have been used to determine the size and shape of reverse micelles formed by these surfactants in water/cyclohexane microemulsions. The luminescence lifetimes of the lanthanide ions have been used to investigate the solvation environment within reverse micelle systems as a function of water content. The use of lanthanide complexes based on 1,4,7,10-tetraazacyclododecane bearing phenanthridine antenna in luminescence microscopy has been explored. Samples such as silica particles, onion skin cells and guinea pig heart cells have been imaged. Time- resolved measurements have allowed time gating of the sample from a fluorescent background and lifetime maps of the images have been obtained. The preparation and characterisation of deuteriated complexes of dota (1,4,7,10- tetraazacyclododecane-1,4,7,10-tetraacetic acid) with lanthanide ions is described. Selective deuteriation of both the ring and arm sites allow the relative quenching effects of C-H/D oscillators to be determined for various lanthanides in a series of structurally well defined complexes. Finally, investigations into the distance dependence of the energy transfer between aromatic chromophores and lanthanide ions have been undertaken. The synthesis of a model system linking a phenanthridine donor to a europium complex by poly(valine) spacer units is described. Preliminary photophysical results show that the quantum yield of emission by europium decreases as the distance between the donor acceptor pair is increased.