<i>N</i>-Aryl Chromophore Ligands for Bright Europium Luminescence

Sterically hindered N-aryl-benzimidazole pyridine-2-carboxylic acids (aryl = phenyl, 4-biphenyl, 2-naphthyl) readily form homoleptic, neutral, nine-coordinate europium complexes which display efficient sensitized luminescence in solid state and in dichloromethane solution with quantum yields reaching 59% and have monoexponential and nearly temperature-independent lifetimes as long as 2.7 ms. The ligand-centered absorption band with a maximum at 321−342 nm and intensity (50−56) × 103 M−1cm−1 ensures efficient harvesting of excitation light by the complexes. Variation of N-aryl chromophore enhances the ligand absorption at 250−350 nm without changing its triplet state energy which amounts to (19.2−21.3) × 103 cm−1. Photophysical properties of europium complexes benefit from adequate protection of the metal by the ligands against non-radiative deactivation and efficient ligand-to-metal energy transfer exceeding 70%. A correlation is observed between the sensitized luminescence quantum yields of europium and the ligand triplet state energy; in certain cases it points to the presence of a second-sphere quenching of EuIII by co-crystallized water in the solid state.