Theoretical and experimental spectroscopic investigation of new Eu(III)-FOD complex containing 2-pyrrolidone ligand

J Mol Model. 2021 Sep 22;27(10):293. doi: 10.1007/s00894-021-04883-1.

Abstract

The preparation and photoluminescent properties of the new [Eu(FOD)3(2-Pyr)2] complex (FOD = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadionate; 2-Pyr = 2-pyrrolidone) are reported. The obtained complex was characterized by elemental analysis, complexometric titration using EDTA, infrared spectroscopy, and single-crystal X-ray diffraction studies. The coordination polyhedron of the complex is described as a distorted square antiprismatic with both 2-Pyr monodentate ligands coordinated to Eu(III) via the oxygen atoms, in neutral form, while the three FOD molecules are coordinated in the anionic form. Structural modeling at the PBE1PBE/SVP/MWB52 level of theory provided a geometry in excellent agreement with the one obtained experimentally. Spectroscopy properties such as intensity parameters (Ω2 and Ω4), radiative emission rate (Arad), and chemical partition of Arad for [Eu(FOD)3(2-Pyr)2] and [Eu(FOD)3(H2O)2] were calculated by using the QDC model with help of the semiempirical wavefunctions. The modeling of the ligand-to-metal energy transfer for both complexes was performed, allowing to obtain the theoretical emission quantum yield and to characterize the most relevant molecular orbitals involved.

Keywords: Energy transfer; Europium complex; LUMPAC; Luminescence.