Polymorphous Indium Metal–Organic Frameworks Based on a Ferrocene Linker: Redox Activity, Porosity, and Structural Diversity

The metallocene-based linker molecule 1,1'-ferrocenedicarboxylic acid (H₂FcDC) was used to synthesize four different polymorphs of composition [In(OH)(FeC₁₂H₈O₄)]. Using conventional solvent-based synthesis methods and varying the synthetic parameters such as metal source, reaction temperature, and solvent, two different MOFs and one 1D-coordination polymer denoted as CAU-43 (<b>1</b>), In-MIL-53-FcDC_a (<b>2</b>), and In-FcDC (<b>3</b>) were obtained. Furthermore, thermal treatment of CAU-43 (<b>1</b>) at 190 °C under vacuum yielded a new polymorph of <b>2</b>, In-MIL-53-FcDC_b (<b>4</b>). Both MOFs <b>2</b> and <b>4</b> crystallize in a MIL-53 type structure, but in different space groups <i>C</i>2/<i>m</i> for <b>2</b> and <i>P</i>1̅ for <b>4</b>. The structures of the four title compounds were determined by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), or a combination of three-dimensional electron diffraction measurements (3D ED) and PXRD. N₂ sorption experiments of <b>1</b>, <b>2</b>, and <b>4</b> showed specific surface areas of 355 m² g^-1, 110 m² g^-1, and 140 m² g^-1, respectively. Furthermore, the electronic properties of the title compounds were characterized via Mössbauer and EPR spectroscopy. All Mössbauer spectra showed the characteristic doublet, proving the persistence of the ferrocene moiety. In the cases of <b>1</b>, <b>3</b>, and <b>4</b>, appreciable impurities of ferrocenium ions could be detected by electron paramagnetic resonance spectroscopy. Cyclovoltammetric experiments were performed to demonstrate the accessible redox activity of the linker molecule of the title compounds. A redox process of FcDC^2- with oxidation (between 0.86 and 0.97 V) and reduction wave (between 0.69 and 0.80 V) was observed.