Mechenochemical synthesis of hexafluorosilicate(SIFSIX)- containing metal-organic framworks (MOFs) Yizhi Xu 1 , Shaodi Li 2 , Hatem M. Titi 2 , Tomislav Friščić 2 and Mihails Arhangelskis 1 1 Faculty of Chemistry, University of Warsaw, Poland, 2 Department of Chemistry, McGill University, Canada Metal-organic frameworks (MOFs) are microporous materials with a wide variety of applications, including gas sorption and separation, catalysis, platforms for artificial photosynthesis and energetic materials 1–3 . The wide range of applications is strictly related to the modular node-and-linker composition, where different combinations of building blocks yield materials with different network topologies and, consequently, properties. Commonly used approaches to MOF synthesis, including solution crystallization and solvothermal synthesis, rely on extensive use of solvents, therefore mechanochemical methods provide a greener approach to making MOFs, that often yields new polymorphs, which are difficult to isolate by solution-based methods. In this presentation we will report mechanochemical synthesis 4 and topological transformation of a series of hexafluorosilicate (SIFSIX) MOFs, a family of MOFs known for excellent gas uptake and selectivity towards carbon dioxide 5 . We have used liquid-assisted grinding (LAG) to synthesize the hygrosopic zinc-based SIFSIX MOF, which yielded a non-porous interpenetrated polymorph initially. In order to obtain the anhydrous, potentially porous Zn SIFSIX polymorph, the sample has been stored under a high temperature environment, resulting in the formation of a previously unknown phase. We will present a combined crystal structure prediction (CSP), X-ray and electron diffraction approach to crystal structure determination of this phase. Moreover, in order to generalize our mechanochemical synthesis approach to obtain porous SIFSIX-containing MOFs, four additional transition metal nodes, namely copper(II), nickel(II), cobalt(II) and manganese(II) have been investigated. Various milling parameters, including nature and quantity of the liquid additives and milling duration have been investigated. Porous framework has been isolated for copper(II) system, demonstrating the possibility of synthesizing porous SIFSIX frameworks by mechanochemical methods. Ultimately, this work can provide us with a more systematic understanding of how to obtain desired SIFSIX MOFs via environmental-friendly mechanochemical synthesis. References 1. Y. Zhang, Y.-Y. Xing, C. Wang, R. Pang, W.-W. Ren, S. Wang, Z.-M. Li, L. Yang, W.-C. Tong, Q.-Y. Wang and S.-Q. Zang, ACS Appl. Mater. Interfaces , , DOI:10.1021/acsami.2c05252. 2. H. M. Titi, J. M. Marrett, G. Dayaker, M. Arhangelskis, C. Mottillo, A. J. Morris, G. P. Rachiero, T. Friščić and R. D. Rogers, Sci. Adv. , 2019, 5 , 1–9. 3. Y. Liu, A. J. Howarth, J. T. Hupp and O. K. Farha, Angew. Chemie Int. Ed. , 2015, 54 , 9001–9005. 4. P. J. Beldon, L. Fábián, R. S. Stein, A. Thirumurugan, A. K. Cheetham and T. Friščić, Angew. Chemie Int. Ed. , 2010, 49 , 9640–9643. 5. S. Ma, B. Space, L. Wojtas, M. Eddaoudi and M. J. Zaworotko, Nature , 2013, 101 , 1–5.
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