Journal article

Mechanochemistry with Metallosupramolecular Polymers

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  • Journal of the American Chemical Society. - American chemical society. - 2014, vol. 136, no. 29, p. 10493-10498
English The transduction of mechanical force into useful chemical reactions is an emerging design approach to impart soft materials with new functions. Here, we report that mechanochemical transductions can be achieved in metallo-supramolecular polymers. We show that both reversible and irreversible reactions are possible and useful to create me-chanically responsive materials that display new functions. The metallopolymer studied was a crosslinked network assembled from a europium salt and a telechelic poly(ethylene-co-butylene) with 2,6-bis(1′- methylbenzimidazolyl)pyridine (Mebip) ligands at the termini. The Eu3+ complexes serve both as mechanically responsive binding motifs and built-in optical probes that can monitor the extent of (dis)assembly due to their characteristic photoluminescent properties. Indeed, dose-dependent and reversible metal-ligand dissociation occurs upon exposure to ultrasound in solution. The absence of ultrasound-induced dissociation of a low-molecular weight model complex and in-depth studies of temperature effects confirm that the dissociation is indeed the result of mechanical activation. The influence of the strength of the metal-ligand interactions on the mechanically induced dissociation was also explored. Metallopolymers in which the Mebip ligands were substituted with more strongly coordinating dipicolinate (dpa) ligands do not dissociate upon exposure to ultrasound. Finally we show that mechanochemical transduction in metallosupramolecular polymers is also possible in the solid state. We demonstrate mending of damaged objects through ultrasound as well as mechanochromic behavior based on metal-exchange reactions in metallopolymers imbibed with an auxiliary metal salt.
Faculté des sciences et de médecine
AMI - Chimie des polymères et matériaux
  • English
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