Redox transformations in electroactive polymer films derived from complexes of nickel with SalEn-type ligands: computational, EQCM, and spectroelectrochemical study
Polymer complexes of nickel with SalEn-type ligands (SalEn = N,N′-bis (salicylidene) ethylenediamine) possess a number of unique properties, such as high redox conductivity, electrochromic behavior and selective catalytic activity in heterogeneous reactions. However, the mechanism of their redox transformation is still not clear. To understand this mechanism, we have performed a combined study of electrochemical and spectral properties of polymers derived from nickel complexes with various SalEn-type ligands containing methoxy substituents in phenyl rings, and methyl substituents in imino bridges. Experimental data were correlated with the results of density functional theory (DFT) calculations for model chains consisting of one to four monomer units. We found that, in acetonitrile-based supporting electrolyte, oxidation of such complexes, regardless of ligand substituents, proceeds via two routes, leading to formation of two oxidized forms: for the first one, a good correlation between experimental and computation results was observed. It has been demonstrated that positive charge in this form is delocalized in the phenyl moieties of ligand. The second oxidized form is stable only in coordinating solvents at high electrode polarizations and is likely to have the charge localized on the central metal atom, stabilized by axial coordination of solvent molecules. The complicated electrochemical response of each of the polymers that we have studied can be explained in the scope of this model without any additional assumptions by taking into account conversion of one oxidized form into another. Understanding the solvent effect on the oxidation route of the complexes will enable controlling their catalytic properties and stability.
KeywordsConductive polymers Cyclic voltammetry Quartz crystal microbalance DFT calculations Voltabsorptometry
This research was supported by the Russian Foundation for Basic Research (grant # 13-03-00843-a). V.V.M. would like to acknowledge the funding from the Russian Foundation for Basic Research (grant # 12-03-00560-a) and St. Petersburg State University (grant # 184.108.40.2062). DFT calculations were performed using the facilities provided by the Computational Resource Center of St. Petersburg State University. The authors wish to thank Prof. Larry Daniels (Wake Forest University, USA) for very constructive comments.
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