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

Jonathan E Halls, A Hernan-Gomez, Andrew D Burrows, Frank Marken

Research output: Contribution to journalArticlepeer-review

44 Citations (Scopus)
171 Downloads (Pure)

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.
Original languageEnglish
Pages (from-to)1475-1480
Number of pages6
JournalDalton Transactions
Volume41
Issue number5
DOIs
Publication statusPublished - 2012

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