Carboxylate anions binding and sensing by a novel tetraazamacrocycle containing ferrocene as receptor

A tetraazamacrocycle containing ferrocene moieties has been synthesized and characterized. The tetraprotonated form of this compound was evaluated as a receptor (R) for anion recognition of several substrates (S), Cl(-), PF(6)(-), HSO(4)(-), H(2)PO(4)(-) and carboxylates, such as p-nitrobenzoate (p-nbz(-)), phthalate (ph(2-)), isophthalate (iph(2-)) and dipicolinate (dipic(2-)). (1)H NMR titrations in CD(3)OD indicated that this receptor is not suitable for recognizing HSO(4)(-) and H(2)PO(4)(-), but weakly binds p-nbz(-), and strongly interacts with ph(2-), dipic(2-), and iph(2-) anions forming 1 : 2 assembled species. The largest beta(2) binding constant was determined for ph(2-), followed by dipic(2-) and finally iph(2-). The effect of the anionic substrates on the electron-transfer process of the ferrocene units of R was evaluated using cyclic voltammetry (CV) and square wave voltammetry (SWV) in methanol solution and 0.1 mol dm(-3)(CH(3))(4)NCl as the supporting electrolyte. Titrations of the receptor were undertaken by addition of anion solutions in their tetrabutylammonium or tetramethylammonium forms. The protonated ligand exhibits a reversible voltammogram, which shifts cathodically in the presence of the substrates. The data revealed kinetic constraints in the formation of the receptor/substrate entity for dipic(2-), ph(2-) and iph(2-) anions, but not for p-nbz(-). In spite of the slow kinetics of assembled species formation with the ph(2-) substrate, this anion provides the largest redox-response when the supramolecular entity is formed, followed by dipic(2-), iph(2-) and finally p-nbz(-) anions. This trend is in agreement with the (1)H NMR results and the values of the binding constants. Single crystal X-ray structures of the receptor with PF(6)(-), ph(2-), iph(2-) and p-nbz(-) were carried out and showed that supermolecules with a RS(2) stoichiometry are formed with the first three anions, but RS(4) with p-nbz(-). In all cases the binding occurs outside the macrocyclic cavity via N-H...O=C hydrogen bonds for carboxylate anions and N-H...F hydrogen bonds for the PF(6)(-) anion, which is in agreement with the solution results. The macrocyclic framework adopts different conformations in order to interact with each substrate having Fe...Fe intramolecular distances ranging from 10.125(14) to 12.783(15)A.