Gadolinium Complex for the Catch and Release of Phosphate from Water

The ability of complexes of hard and labile metal ions with one or more open coordination sites to capture phosphates with high affinity and selectivity directly in water at neutral pH and release them under acidic conditions is evaluated with Gadolinium- 2,2',2''-(((nitrilotris(ethane-2,1-diyl))tris(azanediyl))tris(carbonyl))tris(4-oxo-4H-pyran-3-olate) (Gd-TREN-MAM). This model lanthanide complex has two open coordination sites that, at neutral pH, are filled with water molecules. In water at neutral pH, Gd-TREN-MAM binds phosphate with high affinity (K_a = 1.3 × 10⁴) via the formation of a ternary complex in which one phosphate replaces both inner-sphere water molecules. The formation of this complex is highly pH-dependent; the phosphate is completely released from Gd-TREN-MAM below pH 2. Because the Gd^III ion remains complexed by its ligand, even under strong acidic conditions, Gd-TREN-MAM can be used at least 10 times in a pH-based recycling scheme that enables the catch and release of one phosphate per cycle. Gd-TREN-MAM is highly selective for phosphate over other anions of environmental concerns, including HCO₃^-, HCO₂^-, CH₃CO₂^-, SO₄^2-, NO₃^-, NO₂^-, BrO₃^-, AsO₄^-, F^-, Cl^-, and Br^- and, to a lesser extent, ClO₃^-. The development of such receptors that bind phosphate reversibly in a pH-dependent manner opens the possibility to design catch-and-release systems for the purification of surface waters.