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

Abstract

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.