title: Recognition of oxalate by a copper(II) polyaza macrobicyclic complex.
abstract: A new polyamine macrobicyclic compound was synthesised through a [1+1] "tripod-tripod coupling" strategy and using a Schiff base condensation reaction, followed by sodium borohydride reduction. The resulting compound is a heteroditopic cage (btpN(7)) in which one of the head units is appropriate for the coordination of copper(II), whereas the other head is available for additional hydrogen-bonding and electrostatic interactions with substrates. The acid-base behaviour of the new compound, the stability constants of its complex with the Cu(2+) ion and the association constants of the copper(II) cryptate with oxalate (oxa(2-)), malonate (mal(2-)), succinate (suc(2-)), maleate (male(2-)) and fumarate (fum(2-)) were determined by potentiometry at 298.2 K in aqueous solution and at an ionic strength of 0.10 mol dm(-3) in KNO(3). These studies revealed a clear preference of the receptor [CuH(h)btpN(7)H(2)O]((2+h)+) for oxa(2-) over the other dicarboxylate substrates. This arises from co-operativity between metal-anion coordination and electrostatic and hydrogen-bonding interactions, in accordance with the ideal size of this dicarboxylate, which allow it to take full advantage of the potential binding sites of the receptor. A qualitative indicator-displacement study, in agreement with the potentiometric studies, demonstrated that the copper cryptate receptor can be used as a selective visual sensor for oxalate.
authors.affiliation: Instituto de Tecnologia Química e Biológica, UNL, Av. da República-EAN, 2780-157 Oeiras, Portugal.
authors.forename: Pedro
authors.initials: P
authors.lastname: Mateus
authors.forename: Rita
authors.initials: R
authors.lastname: Delgado
authors.forename: Paula
authors.initials: P
authors.lastname: Brandão
authors.forename: Vítor
authors.initials: V
authors.lastname: Félix
mesh_terms: D000838:Anions / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D047028:Macrocyclic Compounds / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D010070:Oxalates / Q000737:chemistry*; D011073:Polyamines / Q000737:chemistry*
chemical_list: D000838:Anions; D047028:Macrocyclic Compounds; D009942:Organometallic Compounds; D010070:Oxalates; D011073:Polyamines; D003300:Copper