Metal-organic frameworks post-synthetically modified with ferrocenyl groups: framework effects on redox processes and surface conduction

Reference:

Halls, J. E., Hernan-Gomez, A., Burrows, A. D. and Marken, F., 2012. Metal-organic frameworks post-synthetically modified with ferrocenyl groups: framework effects on redox processes and surface conduction. Dalton Transactions, 41 (5), pp. 1475-1480.

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Official URL:

http://dx.doi.org/10.1039/c1dt10734h

Abstract

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.

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