Formation of Heteropolynuclear Lanthanide Complexes Using Macrocyclic Phosphonated Cyclam-Based Ligands

Ligands L₁ and L₂, respectively based on a cyclam and a cross-bridged cyclam scaffold functionalized at N1 and N8 by 6-phosphonic-2-methylene pyridyl groups, are described. While complexation of lanthanide (Ln) cations with L₂ was not possible, a family of complexes has been prepared with L₁, of the general formulae [LnL₁H₂]Cl (Ln³⁺ = Lu, Tb, Yb) or [LnL₁H] (Ln³⁺ = Eu). The solution, structural, potentiometric, and photophysical data for these novel ligands and their complexes have been investigated, including a solid-state study by X-ray diffraction (L₁, L₂, and [EuL₁H]), ¹H NMR complexation investigations (Lu³⁺), as well as UV–vis absorption and luminescence spectroscopy in water and D₂O (pH ≈ 7). L₁ forms 1:1 metal–ligand stoichiometric octadentate complexes in solution. Importantly, the pyridyl phosphonate functions are capable of simultaneous chelation to the metal center and of interaction with a second metal center. ¹H NMR (Lu³⁺) and spectrophotometric titrations of the isolated [TbL₁]⁻ complex by EuCl₃ salts demonstrated the formation of high-order (hetero)­polymetallic species in aqueous solution (H₂O, pH = 7). Global analysis of the luminescence titration experiment points to the formation of 4:1, 3:1, and 3:2 [TbL₁]/Eu heteropolynuclear assemblies, exhibiting a strong preference to forming [TbL₁]₃Eu₂ at increased europium concentrations, with energy transfer occurring between the kinetically inert terbium complex and added europium cations.