Electrochemistry of Polynitrocalix-[4]-arenes

Calix[4]arene is a suitable inert and stable frame for building "smart" molecules and supramolecular assemblies. Polynitrocalix[4]arenes where reducible nitro groups are located at the upper rim are promising precursors for aimed development of sensors. In this work a series of mono-, di-, tri- and tetra nitroderivatives was reduced, the sequence of individual steps was described and the mechanism discussed. It was found that in this molecule with several redox centers all nitro groups are electronically isolated and thus are reduced independently yielding poly-radical ions. Two different couples of equivalent nitro groups were proved in tetranitro derivatives. The experimental results were confirmed by quantum chemical calculations