Eu(III) and Tb(III) Complexes of Octa- and Nonadentate Macrocyclic Ligands Carrying Azide, Alkyne, and Ester Reactive Groups

Azide- and alkyne-functionalized bioconjugable luminescent lanthanide complexes are reported. Reactive handles were introduced into the complexes by the late-stage modification of a methylenecarboxylic acid antenna pendent group. Tb and Eu quantum yields (11–13% and 3.4–3.6%, respectively) were not greatly affected by the presence of the azide or the alkyne compared to the parent complex (ΦTb = 10%, ΦEu = 2.8%). Two avenues were explored for improving the luminescence of the lanthanide (Ln) complexes: (1) attaching the antenna through a tertiary amide linker and (2) replacing a monodentate carboxylate ligand with a bidentate pyridylcarboxylate donor, which yielded a nonadentate ligand that could saturate the lanthanide coordination sphere and eliminate the quenching metal-bound water molecule that was present in the octadentate complexes. The combination of both approaches yielded Eu and Tb emitters with 5.8% and 46% quantum yields. For the Eu complex, this value was the same as ΦEu in the octadentate parent complex. We attribute this to increased photoinduced electron transfer quenching in the nonadentate species, which compensates for the reduced O–H quenching.