Water stability and luminescence of lanthanide complexes of tripodal ligands derived from 1,4,7-triazacyclononane: Pyridinecarboxamide versus pyridinecarboxylate donors

A series of europium(III) and terbium(III) complexes of three 1,4,7-triazacyclononane-based pyridine containing ligands were synthesized. The three ligands differ from each other in the substitution of the pyridine pendant arm, namely they have a carboxylic acid, an ethylamide, or an ethyl ester substituent, i.e., these ligands are 6,6′,6″-[1,4,7- triazacyclononane-1,4,7-triyltris(methylene)]tris[pyridine-2-carboxylic acid] (H₃tpatcn), -tris[pyridine-2-carboxamide] (tpatcnam), and -tris[pyridine-2-carboxylic acid] triethyl ester (tpatcnes) respectively. The quantum yields of both the europium(III) and terbium(III) emission, upon ligand excitation, were highly dependent upon ligand substitution, with a ca. 50-fold decrease for the carboxamide derivative in comparison to the picolinic acid (=pyridine-2-carboxylic acid) based ligand. Detailed analysis of the radiative rate constants and the energy of the triplet states for the three ligand systems revealed a less efficient energy transfer for the carboxamide-based systems. The stability of the three ligand systems in H₂O was investigated. Although hydrolysis of the ethyl ester occurred in H₂O for the [Ln(tpatcnes)](OTf)₃ complexes, the tripositive [Ln(tpatcnam)](OTf) ₃ complexes and the neutral [Ln(tpatcn)] complexes showed high stability in H₂O which makes them suitable for application in biological media. The [Tb(tpatcn)] complex formed easily in H₂O and was thermodynamically stable at physiological pH (pTb 14.9), whereas the [Ln(tpatcnam)](OTf)₃ complexes showed a very high kinetic stability in H₂O, and once prepared in organic solvents, remained undissociated in H₂O.