Mixed-ligand lanthanide complexes supported by ditopic bis(imino-methyl)-phenol/calix[4]arene macrocycles: synthesis, structures, and luminescence properties of [Ln2(L2)(MeOH)2] (Ln = La, Eu, Tb, Yb)

The lanthanide binding ability of a macrocyclic ligand H₆L² comprising two bis(iminomethyl)phenol and two calix[4]arene units has been studied. H₆L² is a ditopic ligand which provides dinuclear neutral complexes of composition [Ln₂(L²)(MeOH)₂] (Ln = La (1), Eu (2), Tb (3), and Yb (4)) in very good yield. X-ray crystal structure analyses for 2 and 3 show that (L²)^6- accommodates two seven coordinated lanthanide ions in a distorted monocapped trigonal prismatic/octahedral coordination environment. UV-vis spectroscopic titrations performed with La³⁺, Eu³⁺, Tb³⁺ and Yb³⁺ ions in mixed MeOH/CH₂Cl₂ solution (I = 0.01 M NBu₄PF₆) reveal that a 2 : 1 (metal : ligand) stoichiometry is present in solution, with log K₁₁ and K₂₁ values ranging from 5.25 to 6.64. The ratio α = K₁₁/K₂₁ of the stepwise formation constants for the mononuclear (L² + M = ML², log K₁₁) and the dinuclear complexes (ML² + M = M₂L², log K₂₁) was found to be invariably smaller than unity indicating that the binding of the first Ln³⁺ ion augments the binding of the second Ln³⁺ ion. The present complexes are less luminescent than other seven-coordinated Eu and Tb complexes, which can be traced to vibrational relaxation of excited Eu^III and Tb^III states by the coligated MeOH and H₂O molecules and/or low-lying ligand-to-metal charge-transfer (LMCT) states.