Tetrazine click as versatile method for covalent post- functionalization of metal-organic frameworks Damian Jędrzejowski and Dariusz Matoga Jagiellonian University in Krakow, Faculty of Chemistry, Krakow, Poland
Modern research in the chemistry of metal-organic frameworks frequently focuses on the multifunctionality of these materials. It is often desirable to combine several properties in one material, allowing it to be used in industry or in a broader scope of applications. [1] One of the ways to obtain a multifunctional material is to modify the pre-assembled frameworks. Among the known classes of post-synthetic modifications, covalent modifications (CPSM) deserve special attention. [2] The variety of functional groups, the possibility to affect the chemical environment of the pores, gentle interference with the crystal structure, and other features of these modifications make us particularly interested in using them in our work.
Fig. 1. Scheme of Inverse-electron-demand Diels-Alder reaction on 1,2,4,5-tetrazine ligand built in a metal-organic framework. The inverse-electron-demand Diels-Alder reaction (iEDDA) is a type of well-known organic reaction that has the advantages of mild synthesis conditions, no (or negligible) byproducts, and high selectivity of the diene in the reaction with the dienophile. At the same time, this reaction has so far been explored to a very small extent for ligands embedded in metal-organic frameworks. This work is a compilation of research on a series of new metal-organic frameworks to apply the iEDDA reaction as an underexplored area of covalent post-synthetic modifications of MOFs. The work includes research on fine-tuning of the flexibility of the JUK-20 material, which is possible on single crystals, and monitoring the reaction using SC-XRD techniques. [3] The topic is extended to pioneering attempts to perform post-synthetic mechanochemical modifications with the iEDDA reaction in order to introduce a specific functional group while maintaining flexibility, and to obtain a functional water vapor sensor with a luminescent response. [4] Research on the use of the iEDDA modification concept in the functionalisation of new materials isostructural to the well-known UiO-68 and MOF-74-III frameworks will also be presented. [5] References 1. The Chemistry of Metal-Organic Frameworks: Synthesis, Characterization and Applications, S. Kaskel, Viley-VCH Verlag &Co. KGaA: Weinheim, 2016; 2. S.M. Cohen, Chem. Rev ., 2012 , 112, 970; 3. D. Jędrzejowski, M. Pander, W. Nitek, W. Bury, D. Matoga, Chem. Mater., 2021 , 33, 7509;
4. D. Jędrzejowski, M. Ryndak, J.J. Zakrzewski, M. Hodorowicz, S. Chorąży, D. Matoga, under review; 5. D. Jędrzejowski, G. Kowacz, M. Pander, E. Stachura, W. Bury, D. Matoga, unpublished results.
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