Synthesis and electrochemical characterisation of benzylmercapto and dodecylmercapto tetra substituted cobalt, iron, and zinc phthalocyanines complexes

The work reports on cyclic voltammetry (CV), square wave voltammetry and spectroelectrochemistry of the following complexes: tetrakis (benzylmercapto) phthalocyanine complexes of Zn(II) (ZnTBMPc, 4a), Co(II) (CoTBMPc, 5a), and Fe(II) (FeTBMPc 6a); tetrakis (dodecylmercapto) phthalocyanine complexes of Zn(II) (ZnTDMPc, 4b), Co(II) (CoTDMPc, 5b), and Fe(II) (FeTDMPc, 6b). More reversible CV couples were observed for complexes 4a, 5a, and 6a containing thiol phenyl ring substituents. Complexes 4b, 5b, and 6b containing long chain thiol substituents showed less reversible couples. Complexes 6a and 6b showed a relatively large number of redox processes (5 for 6a and 6 for 6b) within the potential window employed in this work. The processes for FePc derivatives (6a) are assigned to FeIIIPc−1/FeIIIPc−2, FeIIIPc−2/FeIIPc−2, FeIIPc−2/FeIPc−2, FeIPc−2/FeIPc−3, and FeIPc−3/FeIPc−4 and for the CoPc derivative (5a) to CoIIIPc−1/CoIIIPc−2, CoIIIPc−2/CoIIPc−2, CoIIPc−2/CoIPc−2, and CoIPc−2/CoIPc−3.