Light‐Fueled Transformations of a Dynamic Cage‐Based Molecular System

Autor: Marco Ovalle, Michael Kathan, Ryojun Toyoda, Charlotte N. Stindt, Stefano Crespi, Ben L. Feringa
Přispěvatelé: Synthetic Organic Chemistry, Stratingh Institute of Chemistry
Jazyk: angličtina
Předmět:
Zdroj: Angewandte Chemie-International Edition, 62(9):e202214495. WILEY-V C H VERLAG GMBH
ISSN: 1521-3757
0044-8249
1433-7851
DOI: 10.1002/ange.202214495
Popis: 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.
Databáze: OpenAIRE
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