Contribution of energy transfer from the singlet state to the sensitization of Eu3+ and Tb3+ luminescence by sulfonylamidophosphates.
A series of stable lanthanide complexes Na[Ln(L)4](Ln=La3+,Eu3+,Gd3+,Tb3+,with L=dimethyl(4-methylphe-nylsulfonyl)amidophosphate and dimethyl-2-naphthylsulfo-nylamidophosphate)were synthesized.The compounds were characterized by single-crystalX-raydiffraction, IR, ab-sorption,and emission spectroscopyat 293 and 77 K. In con-trastto the usual and well-known dominant role of the ligand triplet state in intramolecular energy transfer process-es in Ln complexes,in this particular new class of Ln com-pounds with sulphonylamidophosphate ligands, strongex-perimental and detailed theoretical evidence suggest a domi-nantrole is played by the ligand first excited singlet state.The importance of the role played by the 7F5 levelin the caseof the Tb3+compound in this processis shown.Thetheoretical approach for the energy transfer rates was suc-cessfully applied to the rationalization of the experimental data.The higher-lying excited levels of Eu (5DJ,5LJ,5GJ) and Tb (5DJ,5GJ,5LJ,5HJ,5FJ,5IJ)were includedin the calculations for the first time.Both the multipolar and exchange mechanisms were taken into account. The experimental intensity parameters (Wl), emission lifetimes(t), radiative (Arad)and non-radiative(Arad)decay rates, and quantum yields(theo-retical and experimental)were determined and are discussed in detail.
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