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Contribution of Energy Transfer from the Singlet State to the Sensitization of Eu 3+ and Tb 3+ Luminescence by Sulfonylamidophosphates
Author(s) -
Kasprzycka Ewa,
Trush Victor A.,
Amirkhanov Vladimir M.,
Jerzykiewicz Lucjan,
Malta Oscar L.,
Legendziewicz Janina,
Gawryszewska Paula
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201603767
Subject(s) - excited state , intramolecular force , lanthanide , luminescence , singlet fission , singlet state , radiative transfer , chemistry , atomic physics , phosphorescence , ligand (biochemistry) , energy transfer , fluorescence , crystallography , analytical chemistry (journal) , physics , stereochemistry , ion , optics , biochemistry , receptor , organic chemistry , chromatography
A series of stable lanthanide complexes Na[Ln(L) 4 ] (Ln=La 3+ , Eu 3+ , Gd 3+ , Tb 3+ , 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 7 F 5 level in the case of the Tb 3+ 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 ( 5 D J , 5 L J , 5 G J ) and Tb ( 5 D J , 5 G J , 5 L J , 5 H J , 5 F J , 5 I J ) were included in the calculations for the first time. Both the multipolar and exchange mechanisms were taken into account. The experimental intensity parameters (Ω λ ), emission lifetimes (τ), radiative (A rad ) and non‐radiative (A nrad ) decay rates, and quantum yields (theoretical and experimental) were determined and are discussed in detail.