Title :

Synergistic topological and supramolecular control of Diels‐Alder reactivity based on a tunable self‐complexing hos‐guest molecular switch

Author(s) :

Ribeiro, Cedric [Auteur]
Unité Matériaux et Transformations (UMET) - UMR 8207
Cariello, Michele [Auteur]

Malfait, Aurélie [Auteur]
Unité Matériaux et Transformations (UMET) - UMR 8207
Bria, Marc [Auteur]
Institut Michel Eugène Chevreul - FR 2638 [IMEC]
Fournier, David [Auteur]
Unité Matériaux et Transformations (UMET) - UMR 8207
Lyskawa, Joel [Auteur]
Unité Matériaux et Transformations (UMET) - UMR 8207
Le Fer, Gaëlle [Auteur]
Unité Matériaux et Transformations (UMET) - UMR 8207
Potier, Jonathan [Auteur]
Unité Matériaux et Transformations (UMET) - UMR 8207
Hoogenboom, Richard [Auteur]
Universiteit Gent = Ghent University [UGENT]
Cooke, Graeme [Auteur]

Woisel, Patrice [Auteur]
Unité Matériaux et Transformations (UMET) - UMR 8207

Journal title :

Chemistry - A European Journal

Volume number :

e202302300

Publisher :

Wiley

Publication date :

2023-11-22

HAL domain(s) :

Chimie/Polymères

English abstract : [en]

Compartmentalization and binding‐triggered conformational change regulate many metabolic processes in living matter. Here, we have synergistically combined these two biorelevant processes to tune the Diels‐Alder (DA) ...
Show more >Compartmentalization and binding‐triggered conformational change regulate many metabolic processes in living matter. Here, we have synergistically combined these two biorelevant processes to tune the Diels‐Alder (DA) reactivity of a synthetic self‐complexing host‐guest molecular switch CBPQT4+‐Fu, consisting of an electron‐rich furan unit covalently attached to the electron‐deficient cyclobis(paraquat‐p‐phenylene) tetrachloride (CBPQT4+, 4Cl‐) host. This design allows CBPQT4+‐Fu to efficiently compartmentalize the furan ring inside its host cavity in water, thereby protecting it from the DA reaction with maleimide. Remarkably, the self‐complexed CBPQT4+‐Fu can undergo a conformational change through intramolecular decomplexation upon the addition of a stronger binding molecular naphthalene derivative as a competitive guest, triggering the DA reaction upon addition of a chemical regulator. Remarkably, connecting the guest onto a thermoresponsive lower critical solution temperature (LCST) copolymer regulator controls the DA reaction on command upon heating and cooling the reaction media beyond and below the cloud point temperature of the copolymer, representing a rare example of decreased reactivity upon increasing temperature. Altogether, this work opens up new avenues towards combined topological and supramolecular control over reactivity in synthetic constructs enabling control over reactivity through molecular regulators or even mild temperature variations.Show less >

Language :

Anglais

Peer reviewed article :

Oui

Audience :

Internationale

Popular science :

Non

ANR Project :

MultIfunctional and Multi-sTimuli responsive Hydrogels

Administrative institution(s) :

Université de Lille
CNRS
INRAE
ENSCL

Collections :

• Unité Matériaux et Transformations (UMET) - UMR 8207

Research team(s) :

Ingénierie des Systèmes Polymères

Submission date :

2023-12-22T14:51:19Z
2024-01-17T15:26:52Z
2024-02-29T16:46:26Z