New lanthanide complexes containing maltol and bipyridine ligands: Synthesis, solid state characterization,...

Three new lanthanide complexes [Ln(maH)(ma)(bipy)(NO₃)₂](Ln = Gd³⁺, Eu³⁺ or Tb³⁺; maH = maltol, ma = maltolate, bipy = 2,2'-bipyridine) were synthesized and characterized by infrared spectroscopy, powder and single-crystal X-ray diffraction, and thermogravimetric analysis. The complexes crystallize in the monoclinic system, with the Europium complex belonging to space group P21/n, and the Gadolinium and Terbium complexes to P21/c. Each lanthanide center adopts a nine-coordinate geometry, chelated by one bidentate bipyridine, two bidentate nitrate anions, one bidentate maltolate, and one monodentate maltol ligand. The Europium complex was studied from molecular modeling. The WB97XD model was considered suitable for describing both structural and photophysical properties of the complexes. Excited singlet (S₁) and triplet (T₁) ligand states were investigated by time-dependent DFT calculations, and LC-WPBE functional showed good agreement with experimental data. Photoluminescence measurements, including lifetimes and quantum yields, revealed distinct intramolecular energy transfer pathways for the Europium and Terbium complexes. Experimental and theoretical Judd-Ofelt intensity parameters, combined with a proposed Jablonski-type energy diagram, were employed to describe the luminescence properties of the Europium complex. The low emission quantum efficiency of the ⁵D₀ emitting level was attributed to the presence of the ligand-to-metal charge transfer state (LMCT), supported by experimental and theoretical analyses. The proposed kinetic model showed excellent agreement with experimental results. Additionally, the complexes exhibited higher cytotoxic activity against human breast cancer cells (MDA-MB-231) compared with normal human fibroblast cells (NIH-3 T3).