Cobalt(II) and nickel(II) complexes of a cyclam derivative as carriers in iodide-selective electrodes Original Research Article

The ligand 1,4,8-tri(n-octyl)-1,4,8,11-tetraazacyclotetradecane (L1) containing pendant octyl groups has been synthesised. L1 is a tetraazamacrocycle derived from the well-known cyclam unit, and the Ni2+ and Co2+ complexes, [Ni(L1)]2+ and [Co(L1)]2+, have been isolated and characterised. The ability of the nickel(II) and cobalt(II) complexes to act as anion receptors has been studied by using them as ionophores in membrane-based ion-selective electrodes (ISEs). The PVC membrane containing the complex [Ni(L1)]2+ and 2-nitrophenyloctylether as plasticizer shows a Nernstian response against iodide in a concentration range from 1×10−1 to 4×10−5 M I− with a detection limit of 1.6×10−5 M I− and a slope of 58.6 mV/pI− at pH 7 (25 °C). In comparison, the electrode containing [Co(L1)]2+ as ionophore gave a sub-Nernstian slope and a low lifetime. A comparison between the iodide-selective electrode containing [Ni(L1)]2+ and other reported iodide-selective electrodes is also reported.