Mechanochemical self-assembly of cavity-containing anionic salicylic acid-based metallostructures Jean-Louis Do 1,2 , Farshid Effaty 1,2 , Thomas Auvray 2 , Hatem M. Titi 2 , Xavier Ottenwaelder 1 , Louis A. Cuccia 1 , and Tomislav Friščić 2 1 Department of Chemistry and Biochemistry, Concordia University, Canada, 2 Department of Chemistry, McGill University, Canada Supramolecular metallostructures have contributed significantly towards our understanding of self-assembly, molecular recognition, interactions with biologically relevant molecules, catalysis, and design of therapeutics. 1-3 Studies on these materials, however, have largely focused on the synthesis of cationic and neutral systems. The preparation of new and complex anionic structures as functional materials has been scarce and further hindered by the conventional limitations of solution-based chemistry, particularly reactant solubility and the need for varying levels of dilution to achieve high selectivity and obtain crystalline materials. We now describe the potential to exploit mechanochemistry as a mild, rapid, scalable, and environmentally friendly means to access a number of new anionic, salicylic acid-based helicates, pseudohelicates, and cages independent of specialized reaction conditions. 4-6 We demonstrate how these structures can be self-assembled via a ball milling strategy from tri- and tetravalent metal cations in the presence of methylene-bridged salicylic acids using liquid- and ion-and-liquid-assisted grinding (LAG and ILAG, respectively). We demonstrate the different nuances of their self-assembly in solution versus in the solid state, as well as in the presence of various inorganic and organic cations. We further discuss the implications of this mechanochemical methodology on the discovery of new anionic solids and functional materials. References
1. C. Piguet, G. Bernardinelli, and G. Hopfgartner, Chem. Rev. , 1997 , 97 , 2005-2062. 2. Y. Fang, W. Gong, L. Liu, Y. Liu, and Y. Cong, Inorg. Chem. , 2016 , 55, 10102-10105. 3. L. Wang et al. , Chem. Commun. , 2018 , 54 , 2212-2215. 4. J.-L. Do, H. M. Titi, L. A. Cuccia, and T. Friščić, Chem. Commun. , 2021 , 57 , 5143-5146.
5. P. Cucos, M. Pascu, R. Sessoli, N. Avarvari, F. Pointillart, and M. Andruh, Inorg. Chem. , 2006 , 45 , 7035-7037. 6. P. Cucos, L. Sorace, C. Maxim, S. Shova, D. Patroi, A. Caneschi, and M. Andruh, Inorg. Chem. , 2017 , 56 , 11668-11675.
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