A combined electrochemical quartz-crystal microbalance probe beam deflection (EQCM-PBD) study of solvent and ion transfers at a poly[Ni(saltMe)]-modified electrode during redox switching

The oxidative polymerisation of the complex2,3-dimethyl-N,N'-bis-(salicylid ene)butane-2,3-diaminatonickel(II), [Ni(saltMe)], was monitored by the elec trochemical quartz microbalance (EQCM) and crystal impedance techniques. Po lymerisation efficiency was maintained throughout deposition of a film, whi ch behaved rigidly, on the electrode. A combined EQCM-PBD (probe beam defle ction) study of the redox process of the film exposed to a monomer-free sol ution of 0.1 M tetraethylammonium perchlorate (TEAP) in acetonitrile showed an electroneutrality mechanism dominated by anion movement accompanied by co-transfer of solvent above 0.8 V. The individual contributions of all the mobile species involved in the redox switching of the poly[Ni(saltMe)] fil m were determined quantitatively by temporal convolution analysis; the esti mated solution-phase diffusion coefficient of the exchanged species was 1.2 4 x 10(-5) cm(2) s(-1).