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.
Subscribe to Journal
Get full journal access for 1 year
only $9.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Liebau, F. Structural Chemistry of Silicates (Springer, 1985).
Wagler, J., Böhme, U. & Kroke, E. in Functional Molecular Silicon Compounds I (ed. Scheschkewitz, D.) Structure and Bonding Vol. 155, 29–105 (Springer, 2014).
Rosenheim, A., Raibmann, B. & Schendel, G. Über innerkomplexe brenzcatechinate vierwertiger elemente. Z. Anorg. Allg. Chem. 196, 160–176 (1931).
Flynn, J. J. & Boer, F. P. Structural studies of hexacoordinate silicon. Tris(o-phenylenedioxy) siliconate. J. Am. Chem. Soc. 91, 5756–5761 (1969).
Laine, R. M. et al. Synthesis of pentacoordinate silicon complexes from SiO2 . Nature 353, 642–644 (1991).
Herreros, B., Carr, S. W. & Klinowski, J. 5-coordinate Si compounds as intermediates in the synthesis of silicates in nonaqueous media. Science 263, 1585–1587 (1994).
Kinrade, S. D. et al. Stable five- and six-coordinated silicate anions in aqueous solution. Science 285, 1542–1545 (1999).
Schmiederer, T. et al. The E. coli siderophores enterobactin and salmochelin form six-coordinate silicon complexes at physiological pH. Angew. Chem. Int. Ed. 50, 4230–4233 (2011).
Yaghi, O. M. et al. Reticular synthesis and the design of new materials. Nature 423, 705–714 (2003).
Côté, A. P. et al. Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005).
El-Kaderi, H. M. et al. Designed synthesis of 3D covalent organic frameworks. Science 316, 268–272 (2007).
Feng, X., Ding, X. & Jiang, D. Covalent organic frameworks. Chem. Soc. Rev. 41, 6010–6022 (2012).
Blake, A. J. et al. Inorganic crystal engineering using self-assembly of tailored building-blocks. Coord. Chem. Rev. 183, 117–138 (1999).
Moulton, B. & Zaworotko, M. J. From molecules to crystal engineering: supramolecular isomerism and polymorphism in network solids. Chem. Rev. 101, 1629–1658 (2001).
Shea, K. J., Loy, D. A. & Small, J. H. Condensed aryl-bridged siliconates. New ladder and network ionomers. Chem. Mater. 4, 255–258 (1992).
Hahn, F. E., Keck, M. & Raymond, K. N. Catecholate complexes of silicon: synthesis and molecular and crystal structures of [Si(cat)2]·2THF and Li2[Si(cat)3]·3.5dme (cat = catecholate dianion). Inorg. Chem. 34, 1402–1407 (1995).
Cella, J. A., Cargioli, J. D. & Williams, E. A. 29Si NMR of five- and six-coordinate organosilicon complexes. J. Organomet. Chem. 186, 13–17 (1980).
O'Keeffe, M., Peskov, M. A., Ramsden, S. J. & Yaghi, O. M. The reticular chemistry structure resource (RCSR) database of, and symbols for, crystal nets. Acc. Chem. Res. 41, 1782–1789 (2008).
Materials Studio Modelling v. 5.0 (Accelrys, 2009).
Mayo, S. L., Olafson, B. D. & Goddard, W. A. DREIDING: a generic force field for molecular simulations. J. Phys. Chem. 94, 8897–8909 (1990).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104–154119 (2010).
Valiev, M. et al. NWChem: a comprehensive and scalable open-source solution for large scale molecular simulations. Comput. Phys. Commun. 181, 1477–1489 (2010).
Lukose, B., Kuc, A. & Heine, T. The structure of layered covalent-organic frameworks. Chem. Eur. J. 17, 2388–2392 (2011).
Ascherl, L. et al. Molecular docking sites designed for the generation of highly crystalline covalent organic frameworks. Nat. Chem. 8, 310–316 (2016).
Warren, B. E. X-Ray Diffraction (Dover, 1969).
Prill, D., Juhas, P., Schmidt, M. U. & Billinge, S. J. L. Modelling pair distribution functions (PDFs) of organic compounds: describing both intra- and intermolecular correlation functions in calculated PDFs. J. Appl. Cryst. 48, 171–178 (2015).
Prill, D., Juhas, P., Billinge, S. J. L. & Schmidt, M. U. Towards solution and refinement of organic crystal structures by fitting to the atomic pair distribution function. Acta Cryst. A 72, 62–72 (2016).
Hmadeh, M. et al. New porous crystals of extended metal-catecholates. Chem. Mater. 24, 3511–3513 (2012).
Liu, Y. et al. Weaving of organic threads into a crystalline covalent organic framework. Science 351, 365–369 (2016).
Rouquerol, J., Rouquerol, F., Llewellyn, P., Maurin, G. & Sing, K. S. W. Adsorption by Powders and Porous Solids 2nd edn (Academic, 2014).
We thank the European Research Council (ERC) for financial support within the project ORGZEO (Grant Number:278593). Support from the German Science Foundation within the Cluster of Excellence UniCat-Unifying concepts in catalysis is further acknowledged. M.J.B. thanks the Czech Science Foundation (GA CR) for junior grant funding (CAMs: 16-21151Y) and the European Research Council (ERC) for funding under the Starting Grant scheme (BEGMAT: 678462). M.J.B. further acknowledges the Charles University Centre of Advanced Materials (CUCAM) (OP VVV Excellent Research Teams, project number CZ.02.1.01/0.0/0.0/15_003/0000417). We thank Professor Holger Dobbek for his precious help, Professor Matthias Driess and Dr Matthias Thommes for fruitful discussions, and Mrs. Christina Eichenauer, Mrs. Maria Unterweger and Mr. Matthias Trunk for their assistance.
The authors declare no competing financial interests.
About this article
Cite this article
Roeser, J., Prill, D., Bojdys, M. et al. Anionic silicate organic frameworks constructed from hexacoordinate silicon centres. Nature Chem 9, 977–982 (2017). https://doi.org/10.1038/nchem.2771
Ionic covalent organic frameworks for the magnetic solid-phase extraction of perfluorinated compounds in environmental water samples
Microchimica Acta (2021)
Nature Communications (2020)
Nature Communications (2020)