In this work, we report that 2-cyano-2-phenylpropanoic acid and its p-Cl, p-CH3 and p-OCH3 derivatives can be used as chemical fuels to control the geometry of the calix[4]arene scaffold in its cone conformation. It is shown that, under the action of the fuel, the cone calix[4]arene platform assumes a “locked” shape with two opposite aromatic rings strongly convergent and the other two strongly divergent (“pinched cone” conformation). Only when the fuel is exhausted, the cone calix[4]arene scaffold returns to its resting, “unlocked” shape. Remarkably, the duration of the “locked” state can be controlled at will by varying the fuel structure or amount. A kinetic study of the process shows that the consume of the fuel is catalyzed by the “unlocked” calixarene that behaves as an autocatalyst for its own production. A mechanism is proposed for the reaction of fuel consumption.

Time Programmable Locking/Unlocking of the Calix[4]arene Scaffold by Means of Chemical Fuels / Del Giudice, D.; Spatola, E.; Cacciapaglia, R.; Casnati, A.; Baldini, L.; Ercolani, G.; Di Stefano, S.. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - 26(2020), pp. 14954-14962. [10.1002/chem.202002574]

Time Programmable Locking/Unlocking of the Calix[4]arene Scaffold by Means of Chemical Fuels

Casnati A.;Baldini L.
;
2020

Abstract

In this work, we report that 2-cyano-2-phenylpropanoic acid and its p-Cl, p-CH3 and p-OCH3 derivatives can be used as chemical fuels to control the geometry of the calix[4]arene scaffold in its cone conformation. It is shown that, under the action of the fuel, the cone calix[4]arene platform assumes a “locked” shape with two opposite aromatic rings strongly convergent and the other two strongly divergent (“pinched cone” conformation). Only when the fuel is exhausted, the cone calix[4]arene scaffold returns to its resting, “unlocked” shape. Remarkably, the duration of the “locked” state can be controlled at will by varying the fuel structure or amount. A kinetic study of the process shows that the consume of the fuel is catalyzed by the “unlocked” calixarene that behaves as an autocatalyst for its own production. A mechanism is proposed for the reaction of fuel consumption.
Time Programmable Locking/Unlocking of the Calix[4]arene Scaffold by Means of Chemical Fuels / Del Giudice, D.; Spatola, E.; Cacciapaglia, R.; Casnati, A.; Baldini, L.; Ercolani, G.; Di Stefano, S.. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - 26(2020), pp. 14954-14962. [10.1002/chem.202002574]
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11381/2885593
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