The effects of oxygen on the photochemical properties of ruthenium(II) complexes in solution and in polymers are reported. In solution, the complex is actually protected from decomposition by the presence of oxygen as a result of deactivation of the complex by oxygen quenching before it can undergo ligand loss by monomolecular dissociation; however, in polymers, the presence of oxygen increases photochemical decomposition. Singlet molecular oxygen, a product of the oxygen quenching process, may attack the ground state complex or triplet oxygen may directly attack the excited state of the complex. Both mechanisms may be involved in the photodestruction of the complex. The role of oxygen in the photodecomposition was examined by monitoring the photochemical decomposition of various complexes of different singlet oxygen reactivity, as well as absorption and mass spectroscopy studies. It is suggested that in polymers, unlike in solutions, the newly formed reactive singlet oxygen is not able to diffuse away from the complex. The singlet oxygen, trapped in close proximity to the metal complex, has an enhanced opportunity to attack it. This cage effect is supported by studies using tris(1,10-phenanthroline)ruthenium(II) in poly(ethylene glycol) of increasing molecular weight to create an increasingly constraining cage around the complex. Increased poly(ethylene glycol) molecular weight leads to increased oxygen attack of the complex, supporting the cage effect.

In luminescence-based ultrasensitive analysis, such as single-molecule detection by flow cytometry, the luminescence background from impurities present in the solvent or reagents can ultimately determine the detection limits. A simple, versatile method for reducing luminescence background is described. The method is based on photobleaching the reagent stream immediately before it enters the detection flow cell. Dramatic reduction (an order of magnitude or more) of both low-level continuous background and single-molecule fluorescence bursts is demonstrated. Application and enhancements of the technique are discussed.