Potentiometric anion selectivity of polymer-membrane electrodes based on cobalt, chromium, and aluminum salens

Metallo-salens of cobalt(II) (Co-Sal), chromium(III) (Cr-Sal), and aluminum(III) (Al-Sal) are used as the active ionophores within plasticized poly(vinyl chloride) membranes. It is shown that central metal-ion plays a critical role in directing the ionophore selectivity. Polymer-membrane electrodes based on Co-Sal, Cr-Sal, and Al-Sal are demonstrated to exhibit enhanced responses and selectivity toward nitrite/thiocyanate, thiocyanate, and fluoride anions, respectively. The improved anion selectivity of the three ionophore systems is shown to deviate significantly from the classical Hofmeister pattern that is based only on ion lipophilicity. For example, optimized membrane electrodes for nitrite ion based on Co-Sal exhibit logK(Nitrite,Anion)(pot) values of -5.22, -4.66, -4.48, -2.5 towards bromide, perchlorate, nitrate, and iodide anions, respectively. Optimized membrane electrodes based on Co-Sal and Cr-Sal show near-Nernstian responses towards nitrite (-57.9+/-0.9 mV/decade) and thiocyanate (-56.9+/-0.8 mV/decade), respectively, with fast response and recovery times. In contrast, Al-Sal based membrane electrodes respond to fluoride ion in a super-Nernstian (-70+/-3 mV/decade) and nearly an irreversible mode. The operative response mechanism of Co-Sal, Cr-Sal, and Al-Sal membrane electrodes is examined using the effect of added ionic sites on the potentiometric response characteristics. It is demonstrated that addition of lipophilic anionic sites to membrane electrodes based on the utilized metallo-salens enhances the selectivity towards the primary ion, while addition of cationic sites resulted in Hofmeister selectivity patterns suggesting that the operative response mechanism is of the charged carrier type. Electron spin resonance (ESR) data indicates that Co(II) metal-ion center of Co-Sal ionophore undergoes oxidation to Co(III). This process leads to formation of a charged anion-carrier that is consistent with the response behavior obtained for Co-Sal based membrane electrodes.