A macrocyclic ligand as receptor and ZnII-complex receptor for anions in water: Binding properties and crystal structures

摘要

Binding properties of 24,29-dimethyl-6,7,15,16-tetraoxotetracyclo[19.5.5. 05,8.014,17]-1,4,9,13,18,21,24,29-octaazaenatriaconta- δ5,8,δ14,17-diene ligand L towards Zn II and anions, such as the halide series and inorganic oxoanions (phosphate (Pi), sulfate, pyrophosphate (PPi), and others), were investigated in aqueous solution; in addition, the ZnII/L system was tested as a metal-ion-based receptor for the halide series. Ligand L is a cryptand receptor incorporating two squaramide functions in an over-structured chain that connects two opposite nitrogen atoms of the Me2[12]aneN4 polyaza macrocyclic base. It binds ZnII to form mononuclear species in which the metal ion, coordinated by the Me2[12]aneN4 moiety, lodges inside the three-dimensional cavity. ZnII-containing species are able to bind chloride and fluoride at the physiologically important pH value of 7.4; the anion is coordinated to the metal center but the squaramide units play the key role in stabilizing the anion through a hydrogen-bonding network; two crystal structures reported here clearly show this aspect. Free L is able to bind fluoride, chloride, bromide, sulfate, Pi, and PPi in aqueous solution. The halides are bound at acidic pH, whereas the oxoanions are bound in a wide range of pH values ranging from acidic to basic. The cryptand cavity, abundant in hydrogen-bonding sites at all pH values, allows excellent selectivity towards Pi to be achieved mainly at physiological pHa 7.4. By joining amine and squaramide moieties and using this preorganized topology, it was possible, with preservation of the solubility of the receptor, to achieve a very wide pH range in which oxoanions can be bound. The good selectivity towards Pi allows its discrimination in a manner not easily obtainable with nonmetallic systems in aqueous environment. Joining squaramide and polyamine groups in a preorganized macrocyclic system with cage topology gave water-soluble ligand L, which acts as both a metal-ion-based and metal-ion-free anion receptor. Complex [Zn IIL] binds halide ions (picture, left), whereas free L additionally binds several inorganic oxoanions, such as phosphate (picture, right), for which it shows selectivity at a wide range of pH values.