Crystalline frameworks composed of hexacoordinate silicon species have thus far only been observed in a few high pressure silicate phases. By implementing reversible Si-O chemistry for the crystallization of covalent organic frameworks, we demonstrate the simple one-pot synthesis of silicate organic frameworks based on octahedral dianionic SiO6 building units. Clear evidence of the hexacoordinate environment around the silicon atoms is given by 29Si nuclear magnetic resonance analysis. Characterization by high-resolution powder X-ray diffraction, density functional theory calculation and analysis of the pair-distribution function showed that those anionic frameworks-M2[Si(C16H10O4)1.5], where M = Li, Na, K and C16H10O4 is 9,10-dimethylanthracene-2,3,6,7-tetraolate-crystallize as two-dimensional hexagonal layers stabilized in a fully eclipsed stacking arrangement with pronounced disorder in the stacking direction. Permanent microporosity with high surface area (up to 1,276 m2 g-1) was evidenced by gas-sorption measurements. The negatively charged backbone balanced with extra-framework cations and the permanent microporosity are characteristics that are shared with zeolites.

Department of Chemistry Lancaster University Bailrigg Lancaster LA1 4YB UK

Department of Chemistry Technische Universität Berlin BA2 Hardenbergstraße 40 10623 Berlin Germany

European Synchrotron Radiation Facility CS40220 38043 Grenoble Cedex 9 France

Faculty of Science Department of Organic Chemistry Charles University Prague Hlavova 8 128 43 Prague 2 Czech Republic

Institute of Inorganic and Analytical Chemistry Goethe University Max von Laue Str 7 60438 Frankfurt am Main Germany

Institute of Organic Chemistry and Biochemistry ASCR v v i Flemingovo nám 2 166 10 Prague 6 Czech Republic

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