New Insights into the Structure and Properties of Electroactive Polymer Films Derived from [Ni(salen)]

Abstract

Oxidative electrochemical polymerization of ( N, N ‘-ethylenebis(salicylideneaminato)) nickel(II), [Ni(salen)], in acetonitrile/TEAP was reinvestigated. The polymers were characterized by in situ FTIR and UV−visible spectroscopies in order to explore film structure and to clarify the electronic states as a function of the electrochemically controlled applied redox potential; oxidized species involved in polymerization and oxidative switching of the polymer were also assessed by ex situ EPR experiments. Integration of data from all techniques revealed that (a) electropolymerization of [Ni(salen)] is ultimately a ligand-based-process that takes place through a mixture of o - and p -linking of the phenyl rings and (b) poly[Ni(salen)] exhibits physical/chemical properties that cannot be attributed to an aggregation of individual complexes, behaving rather like a polyphenylene compound, with the metal ion acting as a bridge between biphenylene moieties.