A New Macrocyclic Cryptand with Squaramide Moieties: An Overstructured Cu^II Complex That Selectively Binds Halides: Synthesis, Acid/Base‐ and Ligational Behavior, and Crystal Structures

Abstract

The synthesis and characterization of the novel 24,29-dimethyl-6,7,15,16-tetraoxotetracyclo-[19.5.5.0(5,8).0(14,17)]-1,4,9,13,18,21,24,29-octaazaenatriaconta-Delta(5,8),Delta(14,17)-diene (L) are reported. Molecule L incorporates two squaramide functions in a overstructured chain connecting two opposite nitrogen atoms of the Me(2)[12]aneN(4) polyaza macrocyclic base to obtain a cage topology. The basicity and binding properties of L towards Cu(II) were determined by means of potentiometric measurements in aqueous solution (298.1+/-0.1 K, I=0.15 mol dm(-3)). Molecule L behaves as a diprotic base under the experimental conditions employed and forms only mononuclear Cu(II) complexes in which the squaramide moieties are not involved in the stabilization of the metal ion that is stabilized by the amine functions of the polyaza base inside the three-dimensional cavity. The [CuL](2+) species was tested as a host for the series of halide anions. UV-visible spectrophotometric experiments permitted the determination of the addition constants of halides to the Cu(II)-complexed species. The [CuL](2+) species binds the anions F(-), Cl(-), and Br(-) by forming the [CuLX](+) species, but does not bind the biggest I(-) anion. A trend of selectivity as a function of the hydrogen-bonding capability as well as the dimensions of the anion were established; the maximum value of selectivity was for addition of the F(-) anion (log K=4.8). This selectivity is due to the presence of the overstructured chain containing the squaramide groups up to the Me(2)[12]aneN(4) macrocyclic base. The squaramide groups, by providing hydrogen-bond contacts, permit the [CuL](2+) species to selectively bind these anions through the formation of a hydrogen-bond network with F(-) and Cl(-). The crystal structures of the [CuLF](+) and [CuLCl](+) cations support the results obtained in aqueous solution.

Ditopic receptors containing urea groups for solvent extraction of Cu(ii) salts

“…The equilibrium constant determined for the interaction with Cl − (log K 11 = 5.57(2)) is higher than that with Br − (log K 11 = 4.22(3)), which is in agreement with the higher stability of Cu(II) complexes with Cl − and the better hydrogen-bonding acceptor character of Cl − compared to Br − . 33 The association constants determined for the interaction of [CuL 3 (OSMe 2 )] 2+ with Cl − and Br − are lower than those obtained for [CuL 1 (OSMe 2 ) 2 ] 2+ ( Table 3). 6, see also Fig.…”

A Metal–Macrocycle Complex as a Fluorescent Sensor for Biological Phosphate Ions in Aqueous Solution

“…Polyamine 4 was obtained by removal of the p-toluenesulfonyl groups of 3 in H 2 SO 4 [13] and was treated with 9-anthraldehyde to afford the Schiff base, which was directly reduced without purification to afford ligand 1. Ligand 2 was prepared by alkylation of 1,7-dimethylcyclen with 9-chloromethylanthracene (K 2 CO 3 , CH 3 CN).…”

The Squaramide versus Urea Contest for Anion Recognition

“…[10] A further contribution in the field involved the design of a macrotricyclic Cu II cryptate that contained two squaramide moieties capable of including halide ions. [11] Recently, a squaramide-based chloride ion receptor, the anion binding cavity of which can be opened and closed by using carbonyl groups as valves, has been described. [12] In this context, we intend to investigate in detail anionrecognition tendencies of the squaramide subunit, to be compared with those of the urea subunit.…”