Electrochemical, spectroelectrochemical, and dielectric properties of metallophthalocyanines bearing redox active cobalt and manganese metal centres

We report herein the synthesis of symmetrical metallophthalocyanines having cobalt, zinc, and manganese as the metal ions, and having tetrakis(4-phenyl-1,3-thiazole-2-thiolate) groups substituted at the peripheral positions of the phthalocyanine. Electrochemical responses of the complexes were determined with voltammetric and in situ spectroelectrochemical measurements. Cobalt and μ-oxo manganese phthalocyanines (CoPc and μ-oxo MnPc) illustrated metal-based electron transfer reactions in addition to the Pc based reactions. μ-oxo-manganese phthalocyanine exhibited completely different redox properties than those of the monomeric manganese phthalocyanine. Thiazole substituents of the complexes caused oxidative electropolymerisation of the complexes on the working electrode. Electropolymerised μ-oxo manganese phthalocyanine catalyzed oxygen evolution reaction (OER) in basic aqueous solution. The ac behaviour of the tetrasubstituted metallophthalocyanines was studied by impedance spectroscopy technique over a temperature range of 300–450 K and frequency of 100 Hz–13 MHz. The results show that the new compounds exhibit abnormally high dielectric constants even at room temperature. It was concluded that Maxwell–Wagner polarisation is an appropriate model to explain the behaviour of the dielectric function at low frequencies. Frequency dependent measurements revealed that the compounds exhibits non-Debye type relaxation behaviour.