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We have used in situRaman spectroscopy to identify a luminescence quencher formed during organic light-emitting device operation. Raman spectroscopy revealed that oxo-bridged dimerization occurs during the operation of [Ru(bpy)3]2+(PF6−)2 devices, where bpy is 2,2′-bipyridine. Photoluminescence spectroscopy showed that oxo-bridged dimers such as [Ru(bpy)2(H2O)]2O4+(PF6−)4 effectively quench photoluminescence. Comparison of the Raman spectra from devices with the spectra from prepared blended films of [Ru(bpy)3]2+(PF6−)2 and [Ru(bpy)2(H2O)]2O4+(PF6−)4 demonstrated that sufficient dimerization occurs in the device to account for the luminescence quenching observed upon device driving. Dimerization occurred particularly where oxygen and moisture could penetrate the organic film. Dimerization could be a general failure mode of organic electroluminescent devices that incorporate metal complexes. Understanding failure under device-relevant conditions can lead to the development of materials and devices that are intrinsically more resistant to degradation.
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