Synthesis, solid state characterization, theoretical and experimental spectroscopic studies of the new lanthanide complexes

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Molecular and biomolecular spectroscopy, 2023-08, Vol.296, p.122677, Article 122677
• Main Authors: Rodrigues, Fernanda Sodré, da Silva, Victor Agostinho Marques, Segovia, Graziella Borges Queiroz, Bortoluzzi, Adailton João, Cuin, Alexandre, de Souza, Jéssica I.R., da Silva, Juliana A.B., Lourenço da Luz, Leonis, Alves Júnior, Severino, Tonon de Almeida, Eduardo, Camargo, Maryene Alves
• Format: Article
• Language: English
• Subjects: DFT; Lanthanide complexes; Molecular modeling; Photoluminescence; Structure
• ISSN: 1386-1425
• DOI: 10.1016/j.saa.2023.122677

[Display omitted] •Gadolinium Complex, Terbium Complex and Europium Complex.•Structure of Lanthanide Coordination Polymers.•Photoluminescence: lifetime, Judd-Ofelt intensity parameters, quantum yield and LMCT.•Molecular Modeling of structural and luminescent properties, Kinetic Model, DFT. Three new complexes Na[Ln(pic)4]ּ⋅2.5H2O (Ln = Tb, Eu or Gd; pic = picolinate) were synthesized and characterized by infrared spectroscopy, powder X-ray diffraction and thermogravimetric analyses. The molecular structures of the complexes have been determined by single-crystal X-ray diffraction. The three isostructural lanthanide complexes crystalize in the hexagonal system with space group P6122 to Eu complex and Gd complex and space group P6522 to Tb complex. In each of the complexes, the picolinate ligands are bonded to Ln3+ and Na+ ions by different coordination modes promoting polymeric structures. The photoluminescent properties of complexes were studied and combined with theoretical studies using the density functional theory (DFT: B3LYP, PBE1PBE) and the semiempirical method AM1/Sparkle from the single crystal X-ray diffraction structures to assign a suitable model for describing the system. The B3LYP DFT functional was considered the most adequate for providing structural properties of the compounds and for describing luminescence properties. The excited triplet states (T1) and excited singlet states (S1) of the ligand were determined theoretically using Time-dependent DFT calculations (TD-DFT: B3LYP, CAM-B3LYP and LC-wPBE) and INDO/S-CIS, with the best agreement with experimental values obtained from the LC-wPBE DFT functional. The photoluminescent spectra of the complexes and their lifetime measurements were determined indicating that the Eu complex and Tb complex display different intramolecular energy transfer mechanisms with higher efficiency to ligand-to-terbium energy transfer. In addition, the experimental and theorical Judd-Ofelt intensity parameters and quantum yields of the complexes were also determined and discussed besides to a proposed 9-state diagram to describe the luminescence properties of the Eu complex. The low value of emission quantum efficiency of 5D0 emitting level of Eu(III) ion was explained by the presence of the ligand-to-metal charge transfer state (LMCT) evidenced experimentally and theoretically. A good agreement was obtained between the proposed kinetic model and experimental results showing the consistency of the set of rate equ