Solid-state and solution properties of cationic lanthanide complexes of a new neutral heptadentate N4O3 tripodal ligand

The synthesis of the potentially heptadentate ligand tris[6-((2-NN-diethylcarbamoyl)pyridyl)methyl]amine, tpaam, containing three pyridinecarboxamide arms connected to a central nitrogen is described. Lanthanide complexes of this ligand are prepared and characterized. The crystallographic structure of the complexes of three lanthanide ions (La, Nd, Lu) is determined. The lanthanide(III) complexes of tpaam crystallize as monomeric species (in the presence of chloride or iodide counterions) in which the ligand tpaam acts as a N4O3 donor. The crystal structures presented here show that the Ln-O and Ln-N-pyridyl distances in the complexes of tpaam are similar to those found for the tpaa complexes (H(3)tpaa = alpha,alpha',alpha"-nitrilotri (6-methyl-2-pyridinecarboxylic acid) despite the difference in charge. A lengthening of the Ln-N-apical, distance is observed in the tpaam complexes compared to the tpa (tris[(2-pyridyl)methyl]amine) complexes which is more marked for larger lanthanides than for smaller ones. The solution structures of the tpaam complexes were analyzed across the 4f series and compared to the solution structures of the lanthanide complexes of the tetradentate ligand tpa. Proton NMR studies are in agreement with the presence of C-3v, symmetric solution species for both ligands. For the larger lanthanides, the cation moves away from the apical nitrogen compared to the position occupied in tpa complexes, whereas for the smaller lanthanides, the metal ion is located in a similar position for the two ligands. Quite surprisingly, the formation constant of the Eu(tpaam)Cl-3 complex in D2O at 298 K (log beta(110) = 2.34(4)) is very similar to the one reported for Eu(tpa)Cl-3 (log beta(110) = 2.49(4) at 298 K in D2O) indicating that the addition of three amide groups to the ligand tpa does not lead to any increase in stability of the lanthanide complexes of tpaam compared to those of tpa.