A porous and redox active ferrocenedicarboxylic acid based aluminium MOF with a MIL-53 architecture. Issue 44 (31st October 2019)

• Record Type: Journal Article
• Authors: Benecke, Jannik; Mangelsen, Sebastian; Engesser, Tobias A.; Weyrich, Thomas; Junge, Jannik; Stock, Norbert; Reinsch, Helge
• Is Part Of: Dalton transactions. Volume 48:Issue 44(2019)
• Page Start: 16737
• Page End: 16743
• Publication Date: 2019-10-31
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c9dt03489g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A new redox active MOF Al-MIL-53-FcDC based on 1, 1′-ferrocenedicarboxylate exhibits reversible electrochemical activity and permanent porosity. Abstract : A metallocene based linker 1, 1′-ferrocenedicarboxylic acid (H2 FcDC) 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 H2 O, exhibiting a BET surface area of 340 m 2 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 FcDC 2− in Al-MIL-53-FcDC. A reversible oxidation and reduction signal (0.75 V and 0.64 V, respectively, vs. Ag) of FcDC 2− was observed and maintained during forty CV cycles, while the crystallinity of the MOF remained unchanged after the experiment.