Ionic liquid effects on the redox potential of ferrocene

The ionic liquid, IL, dependence of the mid-point potential of the ferrocene|ferrocenium, Fc^0/+, couple versus the decamethylferrocene|decamethylferrocenium, DmFc^0/+, couple was studied in eleven ILs and in dichloromethane with added IL as the supporting electrolyte. The difference in mid-point potential between Fc and DmFc indicates that Fc^0/+ couple is clearly dependent on the IL structure. A variation of about 0.100 V over the range of ILs studied under neat conditions and by ca. 0.050 V when studied in dichloromethane is reported. Meanwhile, a variable potential shift ranging from 0.014 to 0.082 V was observed when data was compared in these two systems (ILs vs. dichloromethane). The effect of water and lithium ion on the Fc^0/+ and DmFc^0/+ redox potential was also evaluated and found to be minimal.