Wydział Chemii

Ewa Kasprzycka

Victor A. Trush

Vladimir M. Amirkhanov

Lucjan B. Jerzykiewicz

Oscar L. Malta

Janina Legendziewicz

Paula Gawryszewska

2017

Chemistry-A European Journal

23

1318-1330

10.1002/chem.201603767

Naukowa

Angielski

Artykuł

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 (⁵D_J,⁵L_J,⁵G_J) and Tb (⁵D_J,⁵G_J,⁵L_J,⁵H_J,⁵F_J,⁵I_J)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 (A_rad)and non-radiative(A_rad)decay rates, and quantum yields(theo-retical and experimental)were determined and are discussed in detail.

energy transfer, lanthanides, luminescence, sulphonylamidophosphates

http://dx.doi.org/10.1002/chem.201603767

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