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Updated: May 13, 2025

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
Published on: January 17, 2020
Endohedral Coordination of Bulky Substrates in Metalloenzyme-Like Organometallic Nanotubes
Thomas Pickl1, Patrick Mollik1, Markus R Anneser1
1Department of Chemistry, Catalysis Research Center (CRC) & TUM School of Natural Sciences, Technical University of Munich, Ernst-Otto-Fischer Str. 1, 85747, Garching, Germany.
Abstract:
Artificial receptors inspired by metalloenzymes share three key properties: a structurally flexible cavity, substrate binding via metal-ligand coordination, and metal-based redox activity. Herein, we report an organometallic nanotube with such features based on our supramolecular pillarplex platform, incorporating eight CuI centers in its cavitand walls. The structurally adaptable cavity of this receptor enables the endohedral coordination of tetrahydrofuran (THF) as a hydrophilic model substrate with remarkable binding affinity despite a steric mismatch between the host and guest. Evidence from SC-XRD, 1H NMR titration in aqueous solution, and DFT modelling confirms that metal-ligand coordination governs substrate binding. Electrochemical analysis of a derived rotaxane reveals metal-centered redox activity.
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