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Mechanostereochemical modulation of polymer mechanical properties.

| Source: Proceedings of the National Academy of Sciences of the United States of America

Stereochemistry profoundly affects the physical and mechanical properties of polymers, illustrated by the contrast between elastic natural rubber ( cis -polyisoprene) and the stiffer, less extensible gutta-percha ( trans -isomer). Traditional stereochemistry such as tacticity and cis / trans isomerism primarily governs polymer properties based on fixed structural or conformational factors. Herein, by incorporating the mechanostereochemistry concept into polymers, we demonstrate a stereochemistry

Stereochemistry profoundly affects the physical and mechanical properties of polymers, illustrated by the contrast between elastic natural rubber ( cis -polyisoprene) and the stiffer, less extensible gutta-percha ( trans -isomer). Traditional stereochemistry such as tacticity and cis / trans isomerism primarily governs polymer properties based on fixed structural or conformational factors. Herein, by incorporating the mechanostereochemistry concept into polymers, we demonstrate a stereochemistry paradigm wherein dynamic isomers dictate material properties, thereby defining the unprecedented transient-stereostructure-efficacy mechanism. Specifically, we engineer two mechanically interlocked networks based on [ c 2]daisy chains, where force-triggered intramolecular motion generates mechanostereoisomers with distinct geometric configurations: [ c 2]Daisy chain 1 in MIN- 1 contracts into a fisherman's knot, whereas [ c 2]daisy chain 2 in MIN- 2 extends into a loop. Due to reduced network elasticity from the loop structure, MIN- 2 exhibits a lower modulus in large-strain shear measurements and less pronounced strain hardening in tensile tests compared to MIN- 1 . Since these mechanostereoisomers are induced by force, material properties show strain-dependent character: both networks perform similarly under small or no strain, but diverge significantly at large strains. Our work expands the conceptual boundaries of polymer stereochemistry and provides insights for designing high-performance materials through stereochemical control.

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