title: Oxo-anion recognition by mono- and bisurea pendant-arm macrocyclic complexes.
abstract: 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 metallomacrocyclic 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.
authors.affiliation: Centro Grandi Strumenti and ‡Dipartimento di Chimica, Università di Pavia , via T. Taramelli 12, 27100 Pavia, Italy.
authors.forename: Massimo
authors.initials: M
authors.lastname: Boiocchi
authors.forename: Maurizio
authors.initials: M
authors.lastname: Licchelli
authors.forename: Michele
authors.initials: M
authors.lastname: Milani
authors.forename: Antonio
authors.initials: A
authors.lastname: Poggi
authors.forename: Donatella
authors.initials: D
authors.lastname: Sacchi
mesh_terms: D019342:Acetic Acid / Q000737:chemistry; D000838:Anions; D019817:Benzoic Acid / Q000737:chemistry; D002224:Carbanilides / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D007700:Kinetics; D008024:Ligands; D047028:Macrocyclic Compounds / Q000737:chemistry*; D008958:Models, Molecular; D010710:Phosphates / Q000737:chemistry*; D019802:Succinic Acid / Q000737:chemistry; D013816:Thermodynamics
chemical_list: D000838:Anions; D002224:Carbanilides; D002264:Carboxylic Acids; D056831:Coordination Complexes; D008024:Ligands; D047028:Macrocyclic Compounds; D010710:Phosphates; D003300:Copper; D019817:Benzoic Acid; D019802:Succinic Acid; D019342:Acetic Acid