A series of stable lanthanide complexes Na[Ln(L) ] (Ln=La , Eu , Gd , Tb , with L=dimethyl(4-methylphenylsulfonyl)amidophosphate and dimethyl-2-naphthylsulfonylamidophosphate) were synthesized. The compounds were characterized by single-crystal X-ray diffraction, IR, absorption, and emission spectroscopy at 293 and 77 K. In contrast to the usual and well-known dominant role of the ligand triplet state in intramolecular energy transfer processes in Ln complexes, in this particular new class of Ln compounds with sulphonylamidophosphate ligands, strong experimental and detailed theoretical evidence suggest a dominant role is played by the ligand first excited singlet state. The importance of the role played by the F level in the case of the Tb compound in this process is shown. The theoretical approach for the energy transfer rates was successfully applied to the rationalization of the experimental data. The higher-lying excited levels of Eu ( D , L , G ) and Tb ( D , G , L , H , F , I ) were included in the calculations for the first time. Both the multipolar and exchange mechanisms were taken into account. The experimental intensity parameters (Ω ), emission lifetimes (τ), radiative (A ) and non-radiative (A ) decay rates, and quantum yields (theoretical and experimental) were determined and are discussed in detail.

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Well-designed Ln compounds are UV converters with extremely high, triplet lifetime dependent emission QY, and show SIM behavior.

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New lanthanide dimethyl‐N‐benzoylamidophosphate (HL) based tetrakis‐complexes NEt4[LnL4] (Ln3+=La, Nd, Sm, Eu, Gd, Tb, Dy) are reported. The complexes are characterized by means of NMR, IR, absorption, and luminescent spectroscopy as well as by elemental, X‐Ray, and thermal gravimetric analyses. The phenyl groups of the four ligands of the complex anion are directed towards one side, while the methoxy groups are directed in the opposite side, which makes the complexes under consideration structurally similar to calixarenes. The effect of changing the alkali metal counterion to the organic cation NEt4+ on the structure and properties of the tetrakis‐complex [LnL4]‐ is analyzed. The complexes exhibit bright characteristic for respective lanthanides luminescence. Rather high intensity of the band of 5D0→7F4 transition, observed in the luminescence spectrum of NEt4[EuL4], is discussed based on theoretical calculations.

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