Versatile pyridine-2,6-bis-tetrazolate scaffolds for the formation of highly luminescent lanthanide complexes

Here we report the straightforward synthesis of the ligands L(tz), L(tzC8), L(tzPEG), L(tzAnis) and L(≡Anis) presenting the same pyridine-bistetrazolate (pytz, L) chelating scaffold but different substituents on the para position of the pyridine ring. Its substitution allows the tuning of the solubility of the LnIII complexes [Ln(Li)3]3(-). These new ligands form homoleptic nona-coordinated LnIII complexes of analogous structure and comparable stability in water and methanol. The derivatization of the para position with triazole and substituted triazole groups does not lead to a significant shift of the absorption window, but a shift of 40 nm is observed in ligand L(≡Anis) due to the presence of the p-ethynyl anisole fragment. The L(tzX) series sensitize well, both the Eu and the Tb ions with quantum yields up to 98% for Tb and 43% for Eu, while the ligand L(≡Anis) sensitizes well Eu (QY of 48%) but cannot sensitize Tb due to the position of its triplet state.