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

Ligands L-1 and L-2, respectively based on a cyclam and a cross-bridged cyclam scaffold functionalized at N-1 and N-8 by 6-phosphonic-2-methylene pyridyl groups, are described. While complexation of lanthanide (Ln) cations with L-2 was not possible, a family of complexes has been prepared with L-1, of the general formulae [LnL(1)H(2)]Cl (Ln(3+) = Lu, Tb, Yb) or [LnL(1)H] (Ln(3+) = 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 (L-1, L-2, and [EuL1H]), H-1 NMR complexation investigations (Lu3+), as well as UV-vis absorption and luminescence spectroscopy in water and D2O (pH approximate to 7). L-1 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. 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](3)Eu-2 at increased europium concentrations, with energy transfer occurring between the kinetically inert terbium complex and added europium cations.