The quenching of the [Ru(bipy)3]2+ by Cu2L2+ was studied and the data were plotted with the Stern-Volmer equation. The plot showed a break and was divided into 2 regions, <0.5 and >0.5 Cu2L2+: [Ru(bipy)3]2+ molar ratio. Quenching above the 0.5 Cu2L2+: [Ru(bipy)3]2+ molar ratio was slower (330 x 10-6 M-1s-1) than the quenching rate reaction below 0.5 ratio (387 x 10-6 M-1s-1). With Cu2L2+ being a dimeric complex the break and differences in the quenching reaction rates can be explained in terms of the stoichiometry. When the Cu2L2+: [Ru(bipy)3]2+ ratio is < 0.5, then each [Ru(bipy)3]2+ can interact with 1 Cu2L2+ dimer. At 0.5 then there is exactly a 1:1 ratio RuII : CuII. Above the 0.5 ratio the [Ru(bipy)3]2+ can interact with maybe only one of the Cu2L2+'s in the dimer, or with a [Ru(bipy)3]2+: Cu2L2+ unit, so the quenching is less efficient.

This thesis describes the synthesis and characterisation of metal complexes that contain chemically reduced bipyridyl ligands. The crystal structures of twenty-six novel complexes are reported alongside detailed discussions on the electronic and spectroscopic effects and trends associated with the different oxidation states within these species. Chapter One introduces the isomers of bipyridine and their redox chemistry, the concept of non-innocent ligands and the spectroscopic techniques that are currently used in determining ligand oxidation states. Subsequently, examples of main group, transition metal, lanthanide and actinide species that contain or may contain reduced forms of the ligand are discussed. Chapter Two details the synthesis and structural characterisation of alkali metal salts of singly and doubly reduced forms of the three commercially available bipyridine isomers. The effects of this reduction are investigated with the aim of developing diagnostic fingerprints for each of the ligand oxidation states. Chapter Three discusses the synthesis of an homologous series of compounds of the form [M(2,2'-bipy)(mes)₂]^n– where M = Cr, Mn, Fe, Co, Ni and n = 0, 1. Trends in magnetism, bonding and electronic structure are investigated with reference to theoretical calculations and the diagnostic fingerprints identified in the previous chapter. Chapter Four describes the synthesis and characterisation of three compounds containing the isostructural motif [Zn₂(4,4'-bipy)(mes)₄]^n– where n = 0, 1, 2. Structural and spectroscopic changes are discussed and com- pared to theoretical calculations. Chapter Five contains descriptions of the spectroscopic techniques employed in the above research and synthesis routes to all compounds featured in this thesis.

No / The multicomponent ternary complex of 4-dimethylaminobenzoic acid (4-DABA), 3,5-dinitrobenzoic acid (3,5-DNBA), and 4,40-bipyridine (BIPY) has been studied by variable temperature X-ray and neutron diffraction. Proton disorder is observed within the 4-DABA homodimers present and quantitatively evaluated from neutron data. The effect of the crystal environment and in particular the pyramidalization of the nitrogen atom within the 4-DABA molecule and the consequential effect on the presence of hydrogen atom disorder are discussed with reference to the previously determined pure 4-DABA structure and the binary cocrystal with 3,5-DNBA.