Structural and electrochemical characterisation of [Pd(salen)]-type conducting polymer films

The oxidative polymerisation of four structurally-related Pd(salen)] complexes and characterisation of the resulting polymeric films by cyclic voltammetry (CV), UV-visible transmission spectroscopy, X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) is reported. The voltammetric technique gives insight into the electrochemical properties of the polymeric films whereas UV-visible spectroscopy is used to characterise the electronic structure of Pd electroactive films, of particular relevance to the type of charge carriers. X-ray techniques (supported by density functional theory, DFT) provide information related to composition and structural features of Pd(salen)] precursors and the resulting polymers. Characterisation of polyPd(salen)] films shows that the electrochemical response of these supramolecular systems is ligand-based and dependent upon substituents in the diimine bridge and aldehyde moieties. XAS measurements near the Pd K-edge demonstrate that polymerisation of the Pd complexes does not change the coordination sphere of the Pd centre; this is consistent with the coupling of monomers units via phenyl rings. As further evidence of ligand-based electrochemical responses, polymer doping does not impart any changes at the Pd centre or its coordination sphere. Compositional analysis by XPS confirms that C: Pd, N: Pd and O: Pd surface atomic ratios do not change significantly from monomer to undoped or doped polymer, except for small variations associated with incorporation of electrolyte and solvent upon polymerisation and polymer oxidation. Overall, the data provide a picture of a polyaromatic delocalised electroactive system, in which the metal atom plays a templating (rather than electroactive) role.