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Polymorphous Indium Metal-Organic Frameworks Based on a Ferrocene Linker: Redox Activity, Porosity, and Structural Diversity
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0002-8956-5897
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Number of Authors: 82020 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 59, no 14, p. 9969-9978Article in journal (Refereed) Published
Abstract [en]

The metallocene-based linker molecule 1,1'-ferrocenedicarboxylic acid (H(2)FcDC) 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 ID-coordination polymer denoted as CAU-43 (1), In-MIL-53-FcDC_a (2), and InFcDC (3) were obtained. Furthermore, thermal treatment of CAU-43 (1) at 190 degrees C under vacuum yielded a new polymorph of 2, In-MIL-53-FcDC_b (4). Both MOFs 2 and 4 crystallize in a MIL-53 type structure, but in different space groups C2/m for 2 and P (1) over bar for 4. 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. N-2 sorption experiments of 1, 2, and 4 showed specific surface areas of 355 m(2) g(-)(1), 110 m(2) g(-1), and 140 m(2) g(-)(1), respectively. Furthermore, the electronic properties of the title compounds were characterized via Mossbauer and EPR spectroscopy. All Mossbauer spectra showed the characteristic doublet, proving the persistence of the ferrocene moiety. In the cases of 1, 3, and 4, 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.

Place, publisher, year, edition, pages
2020. Vol. 59, no 14, p. 9969-9978
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Chemical Sciences
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URN: urn:nbn:se:su:diva-184403DOI: 10.1021/acs.inorgchem.0c01124ISI: 000552287100051PubMedID: 32628458OAI: oai:DiVA.org:su-184403DiVA, id: diva2:1473967
Available from: 2020-10-07 Created: 2020-10-07 Last updated: 2022-02-25Bibliographically approved

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Svensson Grape, ErikInge, A. Ken

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