New polyaminocarboxylate macrocycles containing phenolate binding units: synthesis, luminescent and relaxometric properties of their lanthanide complexes

Abstract

The synthesis of two new polyaminocarboxylate macrocycles incorporating one or two intracyclic phenol units (H₄L¹ and H₈L², respectively) is described. The 12-membered H₄L¹ macrocycle leads to soluble and stable mononuclear Ln^III complexes of [(L¹)Ln(H₂O)₂]⁻ composition (Ln = Eu, Tb and Gd) in aqueous solutions. In Tris buffer (pH 7.4), the [(L¹)Tb(H₂O)₂]⁻ complex displays a suitable efficiency for sensitized emission (η_sens = 48%) and a high luminescence quantum yield (Φ = 22%), which is worthy of note for a bis-hydrated terbium complex. Besides, luminescence experiments show that bidentate endogenous anions (citrate, carbonate, and phosphate) do not displace the two inner-sphere water molecules of this complex. In contrast, the possible presence of LMCT states causes the europium complex to be weakly luminescent. The [(L¹)Gd(H₂O)₂]⁻ complex is characterized by high relaxivity (r^{298 K}₁ = 7.2 s⁻¹ mM⁻¹ at 20 MHz) and a very short water residence time of the coordinated water molecules (τ^{298 K}_M = 9 ns), promising values for the realisation of macromolecular systems with high relaxivities. Thus, the Tb and Gd complexes of the H₄L¹ macrocycle exhibit several improvements in terms of luminescent (lower excitation energy, higher brightness) and relaxometric (shorter τ_M) properties compared to the corresponding LnPCTA complexes, where a phenol moiety substitutes a pyridine ring. On the other hand, the 24-membered H₈L² macrocycle including two phenol units in its structure leads to dinuclear complexes of [(L²)Ln₂]²⁻ composition. Its terbium complex shows a long luminescence lifetime (2 ms) and a high quantum yield (43%) in aqueous solutions, making this compound a new promising candidate for time-resolved applications.