Synthesis and electrochemical properties of new cobalt and manganese phthalocyanine complexes tetra-substituted with 3,4-(methylendioxy)-phenoxy

The synthesis and electrochemical properties of new cobalt and manganese phthalocyanine complexes, tetra-substituted with 3,4-(methylendioxy)-phenoxy at the peripheral (complexes 3 and 5) and non-peripheral (complexes 4 and 6) positions, are reported. Complexes 3 and 4 showed Q-band absorption, in DMF, at 668 and 686 nm, respectively while Q-band due to complexes 5 and 6 appeared at 732 and 760 nm, respectively in CHCl3. All the complexes showed well resolved redox processes attributed to both metal and ring based processes. Complexes 3 and 4 showed four redox processes, labeled I, II, III and IV. For complex 3, process I (CoIPc−2/CoIPc−3) was observed at −1.45 V, II (CoIIPc−2/CoIPc−2) at −0.38 V, III (CoIIIPc−2/CoIIPc−2) at +0.49 V and IV (CoIIIPc−1/CoIIIPc−2) at +0.97 V versus Ag|AgCl. Similar processes were observed for complex 4 at −1.36 V, −0.27 V, +0.56 V, +1.03 V versus Ag|AgCl, respectively. Complexes 5 and 6 showed two redox processes (I and II). For complex 5, these processes appeared at −0.79 V (MnIIPc−2/MnIIPc−3, I) and −0.07 V versus Ag|AgCl (MnIIIPc−2/MnIIPc−2, II), while for complex 6, they were observed at −0.86 V and −0.04 V versus Ag|AgCl. Spectroelectrochemistry was used to probe and confirm the origin of these processes.

Cyclic voltammetry profiles of 1 × 10−3 M of complex 3 in DMF containing 0.1 M TBABF4 supporting electrolyte. Frequency: 10 Hz, amplitude: 50 mV, step potential: 10 mV and scan rate: 100 mV versus Ag|AgCl.Figure optionsDownload as PowerPoint slide