Selective anion sensing based on tetra-amide calix[6]arene derivatives in solution and immobilized on gold surfaces via self-assembled monolayers

Two anion receptors, 1 and 2, based on the calix[6]crown-4 architecture were synthesized and characterized by NMR ((II)-I-1, C-13, COSY), UV-vis, and MALDI-MS. (II)-I-1 NMR measurements demonstrate that receptors 1 and 2 exhibit the highest binding affinity for fluoride ions compared to other anions including Cl-, Br-, NO3-, HSO4-, H2PO4-, and AcO-. The binding constants of 1 with F- and AcO- are 326 (+/- 32) and 238 (+/- 23) M-1, whereas those of 2 with F- and AcO- are 222 (+/- 25) and 176 (+/- 21) M-1. The fluorescent titration of 2 with various anions such as Cl-, Br-, NO3-, HSO4-, and H2PO4- led to essentially no change in excimer emission and a slight enhancement of monomer emission. In contrast, a dramatic change was observed in the fluorescence spectra upon the addition of F- and AcO- to 2. Self-assembled monolayers (SAMs) of 1 were formed on gold surfaces and characterized by reductive desorption and other techniques. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy were used to monitor anion recognition by the SAM-modified gold electrodes. The gold electrodes modified by SAMs of 1, upon binding with the F- anion, exhibit a dramatic increase in charge-transfer resistance (R-ct) values. This is due to the repulsion between the negatively charged electrode surfaces and the negatively charged Fe(CN)(6)(3-/4-) redox probe in the electrolyte solution. In contrast, smaller increases in Rct values were observed in the cases of other monovalent anions investigated.