Light‐Fueled Transformations of a Dynamic Cage‐Based Molecular System
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.
- Standort
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Deutsche Nationalbibliothek Frankfurt am Main
- Umfang
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Online-Ressource
- Sprache
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Englisch
- Erschienen in
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Light‐Fueled Transformations of a Dynamic Cage‐Based Molecular System ; day:19 ; month:01 ; year:2023 ; extent:10
Angewandte Chemie ; (19.01.2023) (gesamt 10)
- Urheber
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Ovalle, Marco
Kathan, Michael
Toyoda, Ryojun
Stindt, Charlotte N.
Crespi, Stefano
Feringa, Ben L.
- DOI
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10.1002/ange.202214495
- URN
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urn:nbn:de:101:1-2023012014201733253693
- Rechteinformation
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Letzte Aktualisierung
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15.08.2025, 07:32 MESZ
Datenpartner
Deutsche Nationalbibliothek. Bei Fragen zum Objekt wenden Sie sich bitte an den Datenpartner.
Beteiligte
- Ovalle, Marco
- Kathan, Michael
- Toyoda, Ryojun
- Stindt, Charlotte N.
- Crespi, Stefano
- Feringa, Ben L.
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