Electropolymerization and electrochemical behavior of nickel Schiff base complexes with different groups between imine linkages

Abstract

Nickel Schiff base complexes Ni(salen), Ni(salphen) and Ni(saldmp) are synthesized and electropolymerized on multiwalled carbon nanotube electrodes. The structures of the three monomers are similar except for the groups between the imine linkages, so the difference in electrochemical behavior can be related to the influence of the groups. Polymerization parameters such as the consumed charge, the apparent surface coverage and the doping level are investigated to elucidate the effects of groups between imine linkages. The results show that poly[Ni(salen)] has higher consumed charge and apparent surface coverage than others, which means that poly[Ni(salen)] can be deposited more easily on the electrodes. While poly[Ni(salphen)] has the highest doping level, there are more electrons transferred per monomer unit, indicating a better capacitance for energy storage. The electrochemical characteristics are also evaluated and the peak potential in cyclic voltammetry plots is about 0.9 V for Ni(salen) and Ni(salphen), and about 0.7 V for Ni(saldmp). The different peak potentials indicate the redox potential will be related to the various groups. Meanwhile the galvanostatic charge/discharge curves display a specific capacitance of about 200 F g⁻¹ for poly[Ni(salphen)], and about 150 F g⁻¹ for poly[Ni(salen)] and poly[Ni(saldmp)]. The variation in electrochemical behavior is mainly caused by the different molecular structure and the groups between imine linkages are the unique differences in structure. So we propose a new electronic transmission mechanism that the electrons will transmit via the Ph–CN–Y–NC–Ph path (Y represents groups between imine linkages), and these groups can provide an electronic transmission path as imine bridges and then influence the electrochemical behavior.