Electropolymerization of Bis(4-cyano-1-pyridinio) Derivatives for the Preparation of Polyviologen Films on Electrodes

Abstract

Abstract Six bis(4-cyano-1-pyridinio) derivatives have been synthesized and deposited onto electrodes by cathodic electropolymerization (ERed = −0.64 — −0.74 V vs. SCE) under basic conditions. The deposited films were constructed of polyviologens that showed characteristic electrochromisms with colorless or slightly yellow to blue- or red-violet. The derivative was reduced to 4-cyano-1,4-dihydro-4-pyridyl radicals, which were coupled successively to form a polyviologen film on the electrode with an elimination of cyanide ions. Characteristically, the polyviologen films deposited by this electropolymerization were insoluble in water and common organic solvents with a spontaneous cross-linking. Especially, a polyanion as a supporting electrolyte forced the polyviologen to form a polyelectrolyte complex in situ. The current efficiency of surface coverage with the polyanion electrolyte (23% in the typical case) was about four-times larger than those with monomeric anions.