Formation of heteropolynuclear lanthanide complexes using macrocyclic phosphonated cyclam-based ligands

Knighton, Richard C., Soro, Lohona K., Troadec, Thibault, Mazan, Valerie, Nonat, Aline M., Elhabiri, Mourad, Saffon-Merceron, Nathalie, Djenad, Saifou, Tripier, Raphael and CharbonniereÌ, L.J. (2020) Formation of heteropolynuclear lanthanide complexes using macrocyclic phosphonated cyclam-based ligands. Inorganic Chemistry, 59 (14), 10311-10327. (doi:10.1021/acs.inorgchem.0c01456).

Abstract

Ligands L1 and L2, respectively based on a cyclam and a cross-bridged cyclam scaffold functionalized at N1 and N8 by 6-phosphonic2-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]), 1 H NMR complexation investigations (Lu3+), as well as UVâ'vis absorption and luminescence spectroscopy in water and D2O (pH ≈ 7). L1 forms 1:1 metalâ'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. 1 H NMR (Lu3+) and spectrophotometric titrations of the isolated [TbL1] â' 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.

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Contributors

Author: Richard C. Knighton

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