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Issue 44, 2019
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A porous and redox active ferrocenedicarboxylic acid based aluminium MOF with a MIL-53 architecture

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Abstract

A metallocene based linker 1,1′-ferrocenedicarboxylic acid (H2FcDC) was used to synthesise the first permanently porous ferrocenedicarboxylate, exhibiting a MIL-53 architecture. This compound Al-MIL-53-FcDC [Al(OH)(FcDC)] is obtained in glass vials under mild synthesis conditions at ≤100 °C and after a short reaction time of 90 min. The crystal structure was determined from powder X-ray diffraction data and the compound shows porosity towards N2 and H2O, exhibiting a BET surface area of 340 m2 g−1. Furthermore, the MOF was characterised via EPR and Mössbauer spectroscopy. The Mössbauer spectrum of Al-MIL-53-FcDC shows a characteristic doublet with an isomeric shift of 0.34 mm s−1 and a quadrupole splitting of 2.39 mm s−1, proving the persistence of the ferrocene moiety. A negligibly small amount of impurities of ferrocenium ions could be detected by EPR spectroscopy as a complementary technique. Cyclic voltammetric experiments demonstrated the accessible redox activity of the linker molecule FcDC2− in Al-MIL-53-FcDC. A reversible oxidation and reduction signal (0.75 V and 0.64 V, respectively, vs. Ag) of FcDC2− was observed and maintained during forty CV cycles, while the crystallinity of the MOF remained unchanged after the experiment.

Graphical abstract: A porous and redox active ferrocenedicarboxylic acid based aluminium MOF with a MIL-53 architecture

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Publication details

The article was received on 28 Aug 2019, accepted on 16 Oct 2019 and first published on 16 Oct 2019


Article type: Paper
DOI: 10.1039/C9DT03489G
Dalton Trans., 2019,48, 16737-16743

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    A porous and redox active ferrocenedicarboxylic acid based aluminium MOF with a MIL-53 architecture

    J. Benecke, S. Mangelsen, T. A. Engesser, T. Weyrich, J. Junge, N. Stock and H. Reinsch, Dalton Trans., 2019, 48, 16737
    DOI: 10.1039/C9DT03489G

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