Mechanochemically Triggered Conformational Reordering via Ion-Regulated Molecular Clutches in Nanoconfined Networks.

Reconciling molecular mobility with structural rigidity remains a fundamental thermodynamic paradox in soft matter mechanics, as traditional static nanoconfinement typically restricts chain dynamics and inevitably leads to brittle failure. Here, we demonstrate an ion-regulated dynamic confinement strategy within 1.5 nm 2D silicate galleries that overcomes this classical trade-off. We reveal that intrinsic sodium ions (Na+) function as dynamic "molecular clutches" at the organic-inorganic interface. Rather than acting as static spacers, these confined ions reshape the interfacial thermodynamic landscape, enabling rapid coordination reconfiguration under extreme mechanical stimuli. This multiscale transformation dissipates extreme impact energy via intramolecular flattening and the formation of a highly ordered sacrificial phase, achieving a theoretically computed local ordering of ∼85% within the nanoconfined galleries under an extreme 90% compressive strain, while maintaining an experimental bulk ordering of ∼19% at the same macroscopic deformation limit (characterized by a highly aligned transition-state orientation angle of 18.3°). Consequently, this supramolecular network sustains a compressive stress of 380 MPa at a 95% strain without catastrophic fragmentation, delivering a volumetric energy dissipation of 68.68 J cm-3 with an energy conversion efficiency of ∼87.8%. This study highlights the potential of nanoconfined ion-mediated mechanochemistry as a versatile design strategy for next-generation materials capable of extreme energy dissipation.