Spring Open Two-plus-Two Electron Storage in a Disulfide-Strapped Methyl Viologen Derivative

The synthesis of a disulfide-strapped viologen derivative is described starting from 4,4′-bipyridinyl-3,3′-diol. The first two one-electron reduction potentials, as determined by cyclic voltammetry, occur at E1/2 = −0.03 V and E1/2 = −0.16 V vs Ag/AgCl. This is accompanied by two more well separated one-electron reductions at E1/2 = −1.26 V and E1/2 = −1.54 V vs Ag/AgCl and the breaking of the disulfide bridge. To alleviate electrostatic repulsion between the two thiolate ions the molecular system must twist or “spring open” to accommodate the final two electrons.