Arel – Investigating [Eu(H2O)9]3+ photophysics and creating a method to by-pass luminescence quantum yield determinations

Lanthanide luminescence has been treated separate from molecular photophysics, although the underlying phenomena are the same. As the optical transitions observed in the trivalent lanthanide ions are forbidden, they do belong to the group that molecular photophysics have yet to conquer, yet the experimental descriptors remains valid. Determining these have proven challenging as full control/knowledge of sample composition is a prerequisite. This has been achieved, and here the luminescence quantum yields (ϕlum), luminescence lifetimes (τobs), oscillator strengths (f ), and the rates of non-radiative (knr) and radiative (kr ≡ A) deactivation of [Eu(H2O)9]3+ was determined for the trigonal tricapped prismatic (TTP) coordination geometry. Further, it was shown that instead of a full photophysical characterization, it is possible to relate changes in transition probabilities to the relative parameter Arel, which does not require reference data. While Arel does not afford comparisons between experiments, it resolves emission intensity changes due to emitter properties—changes in A—from intensity changes due to environmental effects—changes in knr, and differences in the number of photons absorbed. When working with fluorescence this may seem trivial, when working with lanthanide luminescence it is not.