Lanthanide(III) Complexes Based on an 18-Membered Macrocycle Containing Acetamide Pendants. Structural Characterization and paraCEST Properties

We report a detailed investigation of the coordination properties of macrocyclic lanthanide complexes containing a 3,6,10,13-tetraaza-1,8(2,6)-dipyridinacyclotetradecaphane scaffold functionalized with four acetamide pendant arms. The X-ray structures of the complexes with the large Ln(3+) ions (La and Sm) display 12- and 10-coordinated metal ions, where the coordination sphere is fulfilled by the six N atoms of the macrocycle, the four O atoms of the acetamide pendants, and a bidentate nitrate anion in the La3+ complex. The analogous Yb3+ complex presents, however, a 9-coordinated metal ion because one of the acetamide pendant arms remains uncoordinated. H-1 NMR studies indicate that the 10-coordinated form is present in solution throughout the lanthanide series from La to Tb, while the smaller lanthanides form 9-coordinated species. H-1 and Y-89 NMR studies confirm the presence of this structural change because the two species are present in solution. Analysis of the H-1 chemical shifts observed for the Tb3+ complex confirms its D-2 symmetry in aqueous solution and evidences a highly rhombic magnetic susceptibility tensor. The acetamide resonances of the Pr3+ and Tb3+ complexes provided sizable paraCEST effects, as demonstrated by the corresponding Z-spectra recorded at different temperatures and studies on tube phantoms recorded at 22 degrees C.

Automated summary

The coordination properties of macrocyclic lanthanide complexes were investigated, revealing different coordination numbers for large and small Ln(3+) ions. The Tb3+ complex displayed D-2 symmetry and a highly rhombic magnetic susceptibility tensor in aqueous solution. The Pr3+ and Tb3+ complexes showed significant paraCEST effects in solution, as demonstrated by Z-spectra recorded at different temperatures and studies on tube phantoms at 22 degrees C.