History of Cobaltabis(dicarbollide) in Potentiometry, No Need for Ionophores to Get an Excellent Selectivity

This work is a mini-review highlighting the relevance of the θ metallabis(dicarbollide) [3,3′-Co(1,2-C(2)B(9)H(11))(2)](−) with its peculiar and differentiating characteristics, among them the capacity to generate hydrogen and dihydrogen bonds, to generate micelles and vesicles, to be able to be dissolved in water or benzene, to have a wide range of redox reversible couples and many more, and to use these properties, in this case, for producing potentiometric membrane sensors to monitor amine-containing drugs or other nitrogen-containing molecules. Sensors have been produced with this monoanionic cluster [3,3′-Co(1,2-C(2)B(9)H(11))(2)](−). Other monoanionic boron clusters are also discussed, but they are much fewer. It is noteworthy that most of the electrochemical sensor species incorporate an ammonium cation and that this cation is the species to be detected. Alternatively, the detection of the borate anion itself has also been studied, but with significantly fewer examples. The functions of the borate anion in the membrane are different, even as a doping agent for polypyrrole which was the conductive ground on which the PVC membrane was deposited. Apart from these cases related to closo borates, the bulk of the work has been devoted to sensors in which the θ metallabis (dicarbollide) [3,3′-Co(1,2-C(2)B(9)H(11))(2)](−) is the key element. The metallabis (dicarbollide) anion, [3,3′-Co(1,2-C(2)B(9)H(11))(2)](−), has many applications; one of these is as new material used to prepare an ion-pair complex with bioactive protonable nitrogen containing compounds, [YH](x)[3,3′-Co(1,2-C(2)B(9)H(11))(2)](y) as an active part of PVC membrane potentiometric sensors. The developed electrodes have Nernstian responses for target analytes, i.e., antibiotics, amino acids, neurotransmitters, analgesics, for some decades of concentrations, with a short response time, around 5 s, a good stability of membrane over 45 days, and an optimal selectivity, even for optical isomers, to be used also for real sample analysis and environmental, clinical, pharmaceutical and food analysis.