Metal-organic framework (MOF) materials based on zinc(ii) and aluminium(iii) dicarboxylate frameworks with covalently attached ferrocene functional redox groups were synthesised by post-synthetic modification and investigated by voltammetry in aqueous and non-aqueous media. In the voltammetry experiments, ferrocene oxidation occurs in all cases, but chemically reversible and stable ferrocene oxidation without decay of the voltammetric response requires a "mild" dichloroethane solvent environment. The voltammetric response in this case is identified as "surface-confined" with fast surface-hopping of electrons and without affecting the bulk of MOF microcrystals. In aqueous media a more complex pH-dependent multi-stage redox process is observed associated with chemically irreversible bulk oxidation and disintegration of the MOF framework. A characteristic 30 mV per pH unit dependence of redox potentials is observed attributed to a "framework effect": the hydroxide-driven MOF framework dissolution. © 2012 The Royal Society of Chemistry.
CITATION STYLE
Halls, J. E., Hernán-Gómez, A., Burrows, A. D., & Marken, F. (2012). Metal-organic frameworks post-synthetically modified with ferrocenyl groups: Framework effects on redox processes and surface conduction. Dalton Transactions, 41(5), 1475–1480. https://doi.org/10.1039/c1dt10734h
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