Electrochemically Directed Synthesis of Cobalt(ii) and Nickel(ii) TCNQF₂^1-/2-Coordination Polymers: Solubility and Substituent Effects in the TCNQF _n(n = 0, 1, 2, 4) Series of Complexes

The reversible diffusion controlled cyclic voltammetry for the reduction of TCNQF­n0/1-/2- (where n = 0, 1, 2, 4) changes significantly on addition of Co2+ and Ni2+ transition metal ions (M2+) because the kinetics associated with electrocrystallisation of the resulting coordination polymers [M(TCNQF2)2(H2O)2] and [M(TCNQF2)] are rapid on the voltammetric time scale. The voltammetry of solutions containing M2+ and TCNQF­2 was undertaken in acetonitrile (0.1 M Bu4NPF6) at both GC and ITO electrodes. New one electron reduced TCNQF2 materials prepared via electrochemically directed synthesis were shown to have the formula [M(TCNQF2)2(H2O)2], assessed by vibrational (IR and Raman) spectroscopy, elemental analysis and thermogravimetric analysis. The solubility of [Ni(TCNQF2)2(H2O)2] (Ksp = 8.29 × 10-11 M3) was significantly higher than the [Co(TCNQF2)2(H2O)2] (Ksp = 1.43 × 10-11 M3). Cyclic voltammetric data suggest the electrocrystallisation of two phases of [Ni(TCNQF2)2(H2O)2] occurs, which is not evident for [Co(TCNQF2)2(H2O)2]. Electrocrystallisation of the highly insoluble [M(TCNQF2)] was achieved at low M2+ and TCNQF2 concentrations. A comparison with published data on the voltammetry of TCNQF­n (n = 0, 1, 2 and 4) for the series of TCNQF­n (n = 0, 1, 2 and 4) containing M2+ is provided. An assessment of the electronic impact of the fluorine substituent of the underlying redox reactions also is established. Predictions are made for the voltammetric behaviour expected for the other transition metal cations with reduced TCNQFn derivatives.