Oxo-anion recognition by mono- and bisurea pendant-arm macrocyclic complexes

The novel macrocyclic copper(II) complexes
[2]2+ and [3]2+, carrying one or two (nitrophenyl)urea fragments
appended to an azacyclam or diazacyclam framework, exploit the
hydrogen-bond-forming abilities of the urea subunits, along with
the metal−ligand interaction, in the recognition of anionic
species. Equilibrium studies in acetonitrile performed on [2]2+
and [3]2+ show that (nitrophenyl)urea pendant arms strongly
interact with anionic species such as carboxylates and phosphates,
which display both coordinating tendencies toward copper(II)
and good affinity toward urea subunits. Stability constants of the
adducts are considerably higher than those determined for the
interaction of the same anions with a “plain urea” reference
compound, confirming the synergistic action of metallomacro-
cyclic and urea subunits. Complex [2]2+ forms 1:1 adducts with acetate, benzoate, hydrogendiphosphate, and dihydrogen phosphate, while complex [3]2+ interacts with the same anions according to both 1:1 and 1:2 stoichiometries, with the exception of hydrogendiphosphate, which forms only the 1:1 adduct with a distinctly high association constant (log K > 7). Spectrophotometric investigations suggest that oxoanionic species interact with the complexes according to a “bridged” mode, inducing the macrocyclic systems to adopt a scorpionate-like conformation, as confirmed by crystallographic studies on the [3]2+/succinate adduct.