Structural Selectivity of Calix[m]pyrroles[n]furans (m + n = 4) as Ionophores in Ag(I) Ion-Selective Electrodes

A series of octamethylcalixm]pyrrolesn]furans (m + n = 4), such astrans-octamethylcalix2]pyrroles2]furans L ₁ ),cis-octamethylcalix2]pyrroles2]furans (L ₂ ) and octamethylcalix1]pyrrole3]furans (L ₃ ) have been studied as sensors in liquid membrane ion-selective electrodes for Ag(I) ion. The electrode based on L ₁ , trans-N₂O₂ porphyrinogen, gave the best results with a wide working concentration range of 1.0 × 10^-1 - 1.0 × 10^5.6 M and a Nernstian slope of 57.0 mV/decade. This electrode exhibited a fast response time of 30 s and high selectivity over a number of mono-, di- and tri-valent cations, with only Tl(I) and Hg(II) ion interferences. The effect of anion excluders on the performance of the membrane electrodes has been also studied. The electrode based on L ₁ showed no significant potential changes in the range 2.5 < pH < 7.5. The crystalstructure of L ₃ , NO₃ porphyrinogen, was determined by single crystal X-ray analysis. The crystallographic analysis of L ₃ reveals that its structure is a saddle-shaped 1,3-alternate conformation with enough space to accommodate Ag(I) in the three dimensional cavity.