Interaction between nickel hydroxy phthalocyanine derivatives with p-chlorophenol: Linking electrochemistry experiments with theory

In this work the interaction between peripherally (β) substituted nickel tetrahydroxyphthalocyanines (β-NiPc(OH)4 and β-Ni(O)Pc(OH)4) with p-chlorophenol is theoretically rationalised by performing calculations at B3LYP/6-31G(d) level. Density functional theory (DFT) and molecular orbital theory are used to calculate the condensed Fukui function for phthalocyanine derivatives and p-chlorophenol, in order to determine the reactive sites involved when p-chlorophenol is oxidized, and to compare theoretically predicted reactivity to experimentally determined electrocatalytic activity. Electrocatalytic activities of adsorbed NiPc derivatives: ads-α-NiPc(OH)8-OPGE (OPGE = ordinary poly graphite electrode), ads-α-NiPc(OH)4-OPGE and ads-β-NiPc(OH)4-OPGE are compared with those of the polymerized counterparts: poly-α-Ni(O)Pc(OH)8-OPGE, poly-α-NiPc(OH)4-OPGE and poly-β-NiPc(OH)4-OPGE, respectively.