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Endohedral Coordination of Bulky Substrates in Metalloenzyme‐Like Organometallic Nanotubes
Author(s) -
Pickl Thomas,
Mollik Patrick,
Anneser Markus R.,
Sixt Florian,
Geißer Korbinian,
Storcheva Oksana,
Halter Dominik P.,
Pöthig Alexander
Publication year - 2025
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202500775
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 Cu I 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, 1 H 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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