A Walk across the Lanthanide Series: Trend in Affinity for Phosphate and Stability of Lanthanide Receptors from La(III) to Lu(III)

The trend in affinity of two 1,2-hydroxypyridinonate lanthanide(III) receptors - LnIII-2,2-Li-HOPO and LnIII-3,3-Gly-HOPO (LnIII = LaIII, PrIII, NdIII, SmIII, EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII, YbIII, and LuIII) - for phosphate across the series was investigated by luminescence spectroscopy via competition against the central europium(III) analog. Regardless of the ligand, the rare earth receptors display a steep and continuous increase in affinity for their phosphate guest across the series, with the later lanthanides displaying the highest affinity for the oxyanion. This trend mirrors that of the stability of the lanthanide receptors, which also increases significantly and continuously from LaIII to LuIII. For these two ligands, the ionic radius of a rare earth, a parameter directly linked to its Lewis acidity, correlates strongly with its affinity for anions, regardless of whether that anion is the one coordinating it (in this case the 1,2-hydroxypyridinonate ligand) or the guest targeted by the lanthanide receptor (in this case phosphate). These observations are indicative of a lack of steric hindrance for coordination of phosphate. Advantageously, increased efficacy of the lanthanide receptor comes with increased stability. The remarkably high stability of LuIII-2,2-Li-HOPO, combined with its high affinity for phosphate, makes it a particularly promising candidate for translational application to medical or environmental sequestration of phosphate since the higher stability will further reduce the risk of the rare earth leaching during anion separation. The unusually large difference in stability between lanthanide complexes (the LuIII complex of 2,2-Li-HOPO is at least 7 orders of magnitude more stable than the LaIII one) bodes well for potential applications in rare earth separation.