Magnesium(II) polyporphine: The first electron-conducting polymer with directly linked unsubstituted porphyrin units obtained by electrooxidation at a very low potential

Electrooxidation of magnesium(II) porphine, a totally unsubstituted porphyrin, in acetonitrile solution under potentiostatic or potentiodynamic regime leads to a polymer film at the electrode surface. Polymer deposition takes place at extremely low potential, several hundred mV less positive even compared to the deposition potential for pyrrole or EDOT (at identical monomer concentrations) in the same solvent. Film thickness can be controlled by the passed deposition charge. This material and its THF-soluble fraction have been characterized by various electrochemical methods as well as by UV–visible and IR spectroscopies, XPS, XRD and MALDI-TOF techniques. This analysis has allowed us to conclude that the polymer film is composed by chains of Mg porphine building blocks, with single bonds between the neighboring units. In the course of the potential sweep, this polymer film demonstrates a redox response resembling that of polythiophene-coated electrodes. Namely, the film is electroactive and electronically conducting in two potential ranges (p- and n-doping), which are separated by a broad interval where the film possesses a much higher resistance. The polymer may be switched between all these redox states repeatedly by the change of the potential. The film capacitance in the electroactive potential intervals is proportional to the deposition charge.