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RESEARCH ARTICLE
Contents Vol 73(12)

Electrochemically Directed Synthesis of Cobalt(ii) and Nickel(ii) TCNQF21–/2– Coordination Polymers: Solubility and Substituent Effects in the TCNQFn (n = 0, 1, 2, 4) Series of Complexes*

Nguyen T. Vo A B , Alan M. Bond A C and Lisandra L. Martin https://orcid.org/0000-0003-0486-5813 A C
+ Author Affiliations
- Author Affiliations

A School of Chemistry, Monash University, Clayton, Vic. 3800, Australia.

B Current address: Department of Chemistry, The University of Da Nang, University of Education and Science, 459 Ton Duc Thang, Da Nang, Vietnam.

C Corresponding authors. Email: Alan.Bond@monash.edu; Lisa.Martin@monash.edu

Australian Journal of Chemistry 73(12) 1197-1207 https://doi.org/10.1071/CH20187
Submitted: 8 June 2020  Accepted: 17 July 2020   Published: 1 September 2020

Abstract

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.


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