Switchable Redox and Thermo‐Responsive Supramolecular Polymers Based on Cyclodextrin‐Polyoxometalate Tandem

Supramolecular polymers built from stimuli‐responsive host‐guest interactions represent an attractive way of tailoring smart materials. Herein, we exploit the chaotropic effect of polyoxometalates and related host‐guest properties to design unconventional polymer systems with reversible redox and th...

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Bibliographic Details
Published in:Chemistry : a European journal 2024-03, Vol.30 (18), p.e202303815-n/a
Main Authors: Khlifi, Soumaya, Yao, Sa, Falaise, Clément, Bauduin, Pierre, Guérineau, Vincent, Leclerc, Nathalie, Haouas, Mohamed, Salmi‐Mani, Hanene, Roger, Philippe, Cadot, Emmanuel
Format: Article
Language:English
Subjects:
Chemical Sciences
Crosslinking
Cyclodextrin
Cyclodextrins
Dynamic structural analysis
Gels
Hybrid systems
Multiscale analysis
NMR
Nuclear magnetic resonance
polymer
Polymers
polyoxometalates
Polyoxometallates
redox stimuli
Self-assembly
Smart materials
Sol-gel processes
supramolecular assembly
Supramolecular polymers
Viscosity
Viscosity measurement
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Summary:Supramolecular polymers built from stimuli‐responsive host‐guest interactions represent an attractive way of tailoring smart materials. Herein, we exploit the chaotropic effect of polyoxometalates and related host‐guest properties to design unconventional polymer systems with reversible redox and thermo‐responsive sol‐gel transition. These supramolecular networks result from the association of cyclodextrin‐based oligomers and Keggin‐type POMs acting as electro‐active crosslinking agents. The structure and the dynamics of such self‐assembly systems have been investigated using a multiscale approach involving MALDI‐TOF, viscosity measurements, cyclic voltammetry, 1H‐NMR (1D and DOSY), and Small‐Angle X‐ray Scattering. Our results reveal that the chaotropic effect corresponds to a powerful and efficient force that can be used to induce responsiveness in hybrid supramolecular oligomeric systems. The chaotropic behavior of polyoxometalates is exploited as an operating principle to promote a reversible and thermo‐responsive sol‐gel transition of cyclodextrin‐based polymer where supramolecular networking results from the host‐guest interactions between cyclodextrin‐based oligomers and Keggin‐type POMs acting as electro‐active crosslinking agents. This study reveals that the chaotropic effect corresponds to an effective force able to induce responsiveness into supramolecular materials.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202303815