Thermally Activated Photophysical Processes of Organolanthanide Complexes in Solution

The effect of temperature upon the lanthanide luminescence lifetime and intensity has been investigated in toluene solution for the complexes LnPhen(TTA) (Ln = Eu, Sm, Nd, Yb; Phen = 1,10-phenanthroline; TTA = thenoyltrifluoroacetonate). Thermally excited back-transfer to a charge transfer state was found to occur for Ln = Eu and can be explained by lifetime and intensity back-transfer models. The emission intensity and lifetime were also quenched with increasing temperature for Ln = Sm, and the activation energy for nonradiative decay is similar to that for the thermal population of Sm³⁺ excited states. Unusual behavior for lifetime and intensity was found for both Ln = Nd, Yb. The usually assumed equivalence of τ/τ₀ = I/I₀ (where τ is lifetime and I is intensity) does not hold for these cases. We infer that for these lanthanide systems the intensity decreases with temperature in the stage prior to population of the luminescent state. The lifetime changes are discussed.