Reversible soft-mechanochemical control of biaryl conformations through crosslinking in a 3D macromolecular network - Archive ouverte HAL
Journal Articles Angewandte Chemie International Edition Year : 2020

Reversible soft-mechanochemical control of biaryl conformations through crosslinking in a 3D macromolecular network

Abstract

Tuning the dihedral angle (DA) of axially chiral compounds can impact biological activity, catalyst efficiency, molecular motor performance, or chiroptical properties. Herein, we report gradual, controlled and reversible changes in molecular conformation of a covalently linked binaphthyl moiety, within a 3D polymeric network by the application of a macroscopic stretching force. We managed a direct observation of the DA changes by measuring the circular dichroism signal of an optically pure BINOL-crosslinked elastomer network. In accordance with computed spectra, stretching the elastomer resulted in a widening of the DA between naphthyl rings when the BINOL was doubly-grafted to the elastomer network, while no effect was observed when a single naphthyl ring of the BINOL was grafted to the elastomer network. Combining both experimental and theoretical results, we have determined that ~170% extension of the elastomers led to the transfer of a mechanical force to the BINOL moiety of 2.5 kcal*mol-1 *Å-1 (~175 pN) in magnitude and results in the opening of the DA of BINOL up to ~130°.
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Dates and versions

hal-02988194 , version 1 (04-11-2020)

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Julien B Kelber, Amina Bensalah-Ledoux, Sarah Zahouani, Bruno Baguenard, Pierre Schaaf, et al.. Reversible soft-mechanochemical control of biaryl conformations through crosslinking in a 3D macromolecular network. Angewandte Chemie International Edition, 2020, 59 (51), pp.23283-23290. ⟨10.1002/anie.202010604⟩. ⟨hal-02988194⟩
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