The significant role that phosphate plays in environmental
water
pollution and biomedical conditions such as hyperphosphatemia highlights
the need to develop robust receptors that can sequester the anion
effectively and selectively from complex aqueous media. Toward that
goal, four macrocyclic tris-bidentate 1,2-hydroxypyridonate (HOPO)
europium(III) complexes containing either a cyclen, cyclam, TACN,
or TACD ligand cap were synthesized and evaluated as phosphate receptors.
The solubility of EuIII-TACD-HOPO in water was insufficient
for luminescent studies. Whereas EuIII-cyclen-HOPO is eight
coordinate with two inner-sphere water molecules, both EuIII-cyclam-HOPO and EuIII-TACN-HOPO are nine coordinate with
three inner-sphere water molecules, suggesting that the two coordination
states are very close in energy. As observed previously with linear
analogues of tripodal HOPO complexes, there is no relationship between
the number of inner-sphere water molecules and the affinity of the
complex for phosphate. Whereas all three complexes do bind phosphate,
EuIII-cyclen-HOPO has the highest affinity for phosphate
with the anion displacing both of its inner-sphere water molecules.
On the other hand, only one or two of the three inner-sphere water
molecules of EuIII-TACN-HOPO and EuIII-cyclam-HOPO
are displaced by phosphate, respectively. All three complexes are
highly selective for phosphate over other anions, including arsenate.
All three complexes are highly stable. EuIII-cyclen-HOPO
and, to a lesser extent, EuIII-TACN-HOPO are more kinetically
inert than the linear EuIII-Ser-HOPO. EuIII-cyclam-HOPO,
on the other hand, is not. This study highlights the significant effect
that minor changes in the ligand cap can have on both the ligand exchange
rate and affinity for phosphate of tripodal 1,2-dihydroxypyridinonate
complexes.