Listening to Lanthanide Complexes: Determination of the Intrinsic Luminescence Quantum Yield by Nonradiative Relaxation

Abstract

The photophysical properties of lanthanide complexes have been studied extensively; however, fundamental parameters such as the intrinsic quantum yield as well as radiative and nonradiative decay rates are difficult or even impossible to measure experimentally. Herein, a photoacoustic (PA) method is proposed to determine the intrinsic quantum yield of lanthanide complexes with lifetimes in the order of milliseconds. This method is used to determine the intrinsic quantum yields for europium(III)‐containing metallomesogens as well as terbium(III) complexes. The results show that the PA signal is sensitive to both the lifetime and the ratio of the fast‐to‐slow heat component of the samples. It is found that there is an efficient ligand sensitization and a moderate intrinsic quantum yield for the complexes. The intrinsic quantum yield of Eu3+ in the metallomesogens exhibits an obvious increase upon the isotropic liquid to smectic A transition. The proposed PA method is quite simple, and can contribute to a clearer understanding of the photophysical processes in luminescent lanthanide complexes.

Critical Role of Energy Transfer Between Terbium Ions for Suppression of Back Energy Transfer in Nonanuclear Terbium Clusters

“…The other rates k r S1  +  k n r S1  = 3.4 × 10 8  s −1 , k isc s1  = 7.5 × 10 8  s −1 , k r T1  +  k nr T1  = 15000 s −1 , and k r Tb  =  k nr Tb  = 400 s −1 were chosen from previous reports5354. The values of k PSET and k BET are arbitrary and do not affect the qualitative result.…”

Interpretation of europium(III) spectra

“…Only the 5 D 0  7 F 2 transition was considered, because the authors argue that this transition accounts for more than 95 % of the total emission of the complex. Yang et al measured the non-radiative deactivation of europium(III) complexes by a photoacoustic method [775].…”

Listening to Chemical Materials: Determination of the Photophysical Parameters by Photoacoustic Spectroscopy

“…The excited state diagram of Eu(bta) 3 L 2 is schematically shown in Fig. 1 [14]. As there is no photolysis for the sample, energy conservation requires that the energy of incident light absorbed E hν be given by …”