Abstract
In a chemical equilibrium, the formation of high-energy species—in a closed system—is inefficient due to microscopic reversibility. Here, we demonstrate how this restriction can be circumvented by coupling a dynamic equilibrium to a light-induced E/Z isomerization of an azobenzene imine cage. The stable E-cage resists intermolecular imine exchange reactions that would “open” it. Upon switching, the strained Z-cage isomers undergo imine exchange spontaneously, thus opening the cage. Subsequent isomerization of the Z-open compounds yields a high-energy, kinetically trapped E-open species, which cannot be efficiently obtained from the initial E-cage, thus shifting an imine equilibrium energetically uphill in a closed system. Upon heating, the nucleophile is displaced back into solution and an opening/closing cycle is completed by regenerating the stable all-E-cage. Using this principle, a light-induced cage-to-cage transformation is performed by the addition of a ditopic aldehyde.
Original language | English |
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Article number | e202214495 |
Number of pages | 10 |
Journal | Angewandte Chemie - International Edition |
Volume | 62 |
Issue number | 9 |
DOIs | |
Publication status | Published - 20-Feb-2023 |
Keywords
- Dynamic Covalent Chemistry
- Molecular Machines
- Photoswitches
- Self-Assembly
- Out-Of-Equilibrium Chemistry
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CCDC 2210597: Experimental Crystal Structure Determination
Ovalle Martinez, M. (Contributor), Kathan, M. (Contributor), Toyoda, R. (Contributor), Stindt, L. (Contributor), Crespi, S. (Contributor) & Feringa, B. L. (Contributor), Cambridge Crystallographic Data Centre, 1-Oct-2022
DOI: 10.5517/ccdc.csd.cc2d69lj, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc2d69lj&sid=DataCite
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