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

Ribeiro, C. et al. (2024) Synergistic topological and supramolecular control of Diels-Alder reactivity based on a tunable self-complexing host-guest molecular switch. Chemistry: A European Journal, 30(11), e202302300. (doi: 10.1002/chem.202302300) (PMID:37991250)

Abstract

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 to 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.

• Item Type: Articles
• Additional Information: This research was supported by the ANR agency (MISMATCH project, ANR-12-BS08-0005). The Chevreul Institute is thanked for its help in the development of this work through the ARCHI-CM project supported by the "Ministère de l’Enseignement Supérieur de la Recherche et de l’Innovation", the region "Hauts-de-France", the ERDF program of the European Union and the “Métropole Européenne de Lille”. GC thanks the EPSRC (EP/E036244/1).
• Keywords: Chemical reactivity, Diels-Alder reaction, topological chemistry, supramolecular chemistry, host-guest chemistry.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Cooke, Professor Graeme and Cariello, Dr Michele
• Authors: Ribeiro, C., Cariello, M., Malfait, A., Bria, M., Fournier, D., Lyskawa, J., Le Fer, G., Potier, J., Hoogenboom, R., Cooke, G., and Woisel, P.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Chemistry: A European Journal
• Publisher: Wiley
• ISSN: 0947-6539
• ISSN (Online): 1521-3765
• Published Online: 22 November 2023
• Copyright Holders: Copyright © 2023 The Authors
• First Published: First published in Chemistry: A European Journal 30(11):e202302300
• Publisher Policy: Reproduced under a Creative Commons License

Project Code	Award No	Project Name	Principal Investigator	Funder's Name	Funder Ref	Lead Dept
310865		Novel Polymers of Intrinsic Microporosity for use as photonic materials	Graeme Cooke	Engineering and Physical Sciences Research Council (EPSRC)	EP/V027425/1	Chemistry