Controlled Hydrolysis of Phosphate Esters: A Route to Calixarene-Supported Rare-Earth Clusters

Phosphate ester bonds are widely present in nature (e. g. DNA/RNA) and can be extremely stable against hydrolysis without the help of catalysts. Previously, we showed how the combination of phosphoryl and calix[4]arene moieties in the same organic framework (L_PO ) allows isolation of single lanthanide (Ln) metal ions as [Ln^III (L_PO )₂ ](O₃ SCF₃ )₃ . Here we report how by controlling the reaction conditions a new hydrolyzed phosphoryl-calix[4]arene ligand (H₃ L_HPO ) is formed as a result of Ln^III -mediated P-OEt bond cleavage in three out of the eight possible sites in L_PO . The chelating nature of H₃ L_HPO traps the Ln^III species in the form of [Ln^III (L_HPO )((EtO)₂ P(O)OH)]₂ dimers (Ln=La, Dy, Tb, Gd), where the Dy derivative shows slow magnetization relaxation. The strategy presented herein could be extended to access a broader library of hydrolyzed platforms (H_x L_HPO ; x=1-8) that may represent mimics of nuclease enzymes.