A Para-Substituted 2-Phenoxy-1,10-Phenanthroline Ligand for Lanthanide Sensitization: Asymmetric Coordination and Enhanced Emission from Eu3+, Tb3+, Sm3+ and Dy3+ Complexes

A para-substituted 1,10-phenanthroline ligand, 2-(4-methylphenoxy)-1,10-phenanthroline (L24), was synthesized and structurally characterized. Complexes with Eu³⁺, Tb³⁺, Sm³⁺, and Dy³⁺ were obtained in a 2:1 ligand-to-metal ratio and analyzed using single-crystal x-ray diffraction, photoluminescence spectroscopy, and TD-DFT calculations. Coordination via the phenanthroline nitrogen atoms, combined with steric asymmetry from the para-methylphenoxy group, induces low-symmetry environments favorable for electric-dipole transitions. Excited-state lifetimes reached 2.12 ms (Eu³⁺) and 1.12 ms (Tb³⁺), with quantum yields of 42% and 68%, respectively. The triplet-state energy of L24 (22,741 cm^-1) aligns well with emissive levels of Eu³⁺ and Tb³⁺, consistent with Latva's criterion. Fluorescence titrations indicated positively cooperative complexation, with association constants ranging from 0.60 to 1.67. Stark splitting and high ⁵D₀ → ⁷F₂/⁷F₁ intensity ratios (R₂ = 6.25) confirm the asymmetric coordination field. The para-methylphenoxy substituent appears sufficient to lower coordination symmetry and strengthen electric-dipole transitions, offering a controlled route to enhance photoluminescence in Eu³⁺ and Tb³⁺ complexes.