The mechanism of quenching of the lanthanide excited state for optical probes using sensitised emission.

The mechanism of quenching of the excited state of terbium and europium complexes by electron-rich reductants occurs by formation of an exciplex involving the triplet excited state of the sensitising chromophore.

A mechanistic study of the dynamic quenching of the excited state of europium(III) and terbium(III) macrocyclic complexes by charge- or electron transfer.

Dynamic quenching of the metal-based excited state of Eu(III) and Tb(III) complexes of sixteen different macrocyclic ligands has been studied. Quenching by urate, ascorbate and selected catechols is most effective for Tb(III) systems, and involves intermediate formation of an excited state complex (exciplex) between the electron-poor heterocyclic sensitising moiety incorporated into the ligand (tetraazatriphenylene, azaxanthone or a pyrazoyl-azaxanthone) and the electron-rich reductant. The process is sensitive to steric inhibition created by the local ligand environment; quenching is reduced as temperature increases as exciplex formation is entropically disfavoured. In contrast, iodide quenches each complex studied according to a classical collisional encounter model; increasing temperature enhances the rate of quenching, and the process is more sensitive to local electrostatic fields generated by ligand substitution, conforming to a traditional Stern-Volmer kinetic model. Quenching may be inhibited by protein association, allowing the identification of candidates for use as optical imaging probes in cellulo.

A ratiometric and non-enzymatic luminescence assay for uric acid: differential quenching of lanthanide excited states by anti-oxidants.

The excited states of Tb and Eu complexes of a common macrocyclic ligand are quenched preferentially by electron transfer from the urate anion, allowing the creation of a new assay to measure uric acid in biological fluids.

Azaxanthones and azathioxanthones are effective sensitisers for europium and terbium luminescence.

Several azaxanthone and azathioxanthone sensitising chromophores have been incorporated into macrocyclic ligands and form well-defined Eu and Tb complexes in polar media. Excitation of the heterocyclic chromophore in the range 330 to 382 nm leads to modest amounts of aromatic fluorescence and relatively efficient metal-based luminescence, with absolute metal-based quantum yields of up to 24% in aqueous media.