Molecular engineering of mechanophore activity for stress-responsive polymeric materials

Brown, Cameron L.; Craig, Stephen L.

doi:10.1039/c4sc01945h

Cited by 124 publications

(136 citation statements)

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“…Covalent polymer mechanochemistry12345 has been extensively explored in recent years for a variety of purposes, including biasing reaction pathways6789, trapping transition states and intermediates1011, catalysis12131415, release of small molecules and protons161718, stress reporting19202122, stress strengthening222324 and soft devices2526. These efforts are largely facilitated by the fact that, unlike other energy sources, mechanical force is directional and regulated by local molecular structure.…”

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Mechanical gating of a mechanochemical reaction cascade

et al. 2016

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Covalent polymer mechanochemistry offers promising opportunities for the control and engineering of reactivity. To date, covalent mechanochemistry has largely been limited to individual reactions, but it also presents potential for intricate reaction systems and feedback loops. Here we report a molecular architecture, in which a cyclobutane mechanophore functions as a gate to regulate the activation of a second mechanophore, dichlorocyclopropane, resulting in a mechanochemical cascade reaction. Single-molecule force spectroscopy, pulsed ultrasonication experiments and DFT-level calculations support gating and indicate that extra force of >0.5 nN needs to be applied to a polymer of gated gDCC than of free gDCC for the mechanochemical isomerization gDCC to proceed at equal rate. The gating concept provides a mechanism by which to regulate stress-responsive behaviours, such as load-strengthening and mechanochromism, in future materials designs.

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“…These efforts are largely facilitated by the fact that, unlike other energy sources, mechanical force is directional and regulated by local molecular structure. Even reactions with very similar intrinsic activation barriers can have very different force-coupled reactivities as a result of the structure of the handle through which force is delivered38272829.…”

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“…[1][2][3][4][5][6][7] One important subset of dynamic mechanical properties is the self-healing ability after mechanical damages. [8][9][10][11][12][13][14][15][16] The combination of mechanophore with luminescence can further endow materials with selfreporting damage detection property [17][18][19] and novel bio-mimic electronics with multifunctionalities. 20,21 The macroscopic dynamic mechanical properties of materials rely on the incorporated dynamic bonding at molecular levels.…”

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The effects of counter anions on the dynamic mechanical response in polymer networks crosslinked by metal–ligand coordination

Rao¹,

Feig²,

Gu³

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Metal-ligand coordination has been proven to be an attractive strategy to tune a polymer network's dynamic mechanical properties, such as self-healing ability. Nonetheless, the role of counter anions is often overlooked. To address this, a series of polydimethylsiloxane (PDMS) 3 showed improved interaction strength with bipyridine ligands. Surprisingly, the addition of Eu(OTf) 3 and Tb(OTf) 3 salts also increased the d-spacing distances of the phase-segregated domains between metal-ligand complexes and the PDMS polymer backbone. For the Eu(OTf) 3 -, Tb(OTf) 3 -PDMS films, the muchimproved self-healing abilities are attributed to the crosslinker dynamics and the enhanced chain mobility. This work underlines the importance of counter anions on the mechanical properties, and provides further guidance on the future design of self-healing metal2ligand crosslinked polymers.) V C 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3110-3116

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“…Load-induced fragmentation of polymers was discovered almost as soon as the nature of polymers had been recognized [2]. Polymer mechanochemistry is thought to be an important (but poorly understood) determinant of how polymeric materials respond to mechanical loads [3][4][5]. Because polymers are subject to such loads throughout their lifecycles, from production to recycling, polymer mechanochemistry pervades our everyday lives.…”

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Polymer Mechanochemistry

2015

Topics in Current Chemistry

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Molecular engineering of mechanophore activity for stress-responsive polymeric materials

Abstract: Molecular-level design principles by which to engineer enhanced mechanophore activity are reviewed, with an emphasis on quantitative structure–activity studies determined for a family of gem-dihalocyclopropane mechanophores.

Cited by 124 publications

References 52 publications

Mechanical gating of a mechanochemical reaction cascade

Mechanical gating of a mechanochemical reaction cascade

The effects of counter anions on the dynamic mechanical response in polymer networks crosslinked by metal–ligand coordination

Polymer Mechanochemistry

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