Inorganic Chemistry, Vol.47, No.11, 4808-4816, 2008
Redox active cage for the electrochemical sensing of anions
The tripodal system [1](3+) forms a 1:1 complex with Coll in which the metal is octahedrally coordinated by three bpy fragments. The [Co-II(1)](5+) Complex provides a cavity suitable for solvent or anion inclusion. X-ray diffraction studies on the crystalline complex salt of formula [Co-II(1)center dot center dot center dot H2O]Cl(PF6)(4)center dot 2MeCN have shown that a water molecule is included in the cavity and the water oxygen atom receives six H-bonds from the C-H fragments of the three imidazolium subunits and of the three proximate pyridine rings, according to a slightly distorted trigonal prismatic geometry. Anion inclusion in an aqueous MeCN solution induces a distinct cathodic shift of the potential of the Co-III/Co-II couple, whose magnitude decreases along the series: Cl- > Br- similar to NCO- > I- similar to NCS-, which reflects anion tendencies to receive H-bonds from the receptor. The variation of the water content in the MeCN solution(from 0 to 20%) induces a gradual change of the voltammetric response to anion titration: from two well distinguished peaks at a fixed potential to a single peak progressively shifted to a more cathodic potential. Such a behavior parallels the gradual decrease of the equilibrium constant for anion inclusion into the [Co-II(1)](5+) receptor.