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Dihydroxybenzoquinone as Linker for the Synthesis of Permanently Porous Aluminum Metal-Organic Frameworks
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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Number of Authors: 6
2016 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 55, no 15, 7425-7431 p.Article in journal (Refereed) Published
Abstract [en]

Two new dihydroxybenzoquinone-based metal-organic frameworks, ((CH3)(2)NH2)(3)[Al-4(L1)(3)(L1(center dot))(3)]center dot 3DMF (1, denoted CAU - 20) and ((CH3)(2)NH2)(3)[Al-4(L2)(3)(L2 center dot)(3)]center dot 9DMF (2, denoted CAU-20-Cl-2), were synthesized at 120 degrees C in PAU using 2,5-dihydroxy-p-benzoquinone ((C6H2(OH)(2)(O)(2)), H(2)L1) and 2,5-dichloro-3,6-dihydroxy-p-benzoquinone ((C6Cl2(OH)(2)(O)(2)), H(2)L2), respectively. Compared to other Al-MOFs, which contain carboxylate or phosphonate groups that connect the metal sites, in 1 and 2 the Al3+ are coordinated by oxido groups. The metal ions are octahedrally surrounded by oxygen atoms Of the deprotonated linker molecules to generate honeycomb layers with a metal to linker ratio of Al: L1/L2 = 2:3. The layers contain L1(2-) and L2(2-) ions as well as linker radical ions L1(center dot 3-) and L2(center dot 3-) in a molar ratio of 1 to 1. The presence of radical ions was confirmed by EPR and UV-vis-spectroscopic Measurements, and the composition was determined from a combination of PXRD, H-1, NMR, TG, and elemental analyses. Charge balance is accomplished through intercalation of (CH3)(2)NH2+ ions which are formed by partial hydrolysis of DMF. In the structures of 1 and 2 the eclipsed layers are AA and ABAB stacked, respectively, and one-dimensional hexagonal channels with diameters of ca. 9 and 6 angstrom are formed. Both compounds exhibit permanent porosity and have specific surface areas of 1440 and 1430 m(2) g(-1), respectively.

Place, publisher, year, edition, pages
2016. Vol. 55, no 15, 7425-7431 p.
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Chemical Sciences
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URN: urn:nbn:se:su:diva-134451DOI: 10.1021/acs.inorgchem.6b00661ISI: 000380864900033PubMedID: 27427885OAI: oai:DiVA.org:su-134451DiVA: diva2:1033836
Available from: 2016-10-10 Created: 2016-10-06 Last updated: 2017-11-30Bibliographically approved

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