The cascade unzipping of ladderane reveals dynamic effects in mechanochemistry

Force can induce remarkable non-destructive transformations along a polymer, but we have a limited understanding of the energy transduction and product distribution in tandem mechanochemical reactions. Ladderanes consist of multiple fused cyclobutane rings and have recently been used as monomeric motifs to develop polymers that drastically change their properties in response to force. Here we show that [4]-ladderane always exhibits ‘all-or-none’ cascade mechanoactivations and the same stereochemical distribution of the generated dienes under various conditions and within different polymer backbones. Transition state theory fails to capture the reaction kinetics and explain the observed stereochemical distributions. Ab initio steered molecular dynamics reveals unique non-equilibrium dynamic effects: energy transduction from the first cycloreversion substantially accelerates the second cycloreversion, and bifurcation on the force-modified potential energy surface leads to the product distributions. Our findings illustrate the rich chemistry in closely coupled multi-mechanophores and an exciting potential for effective energy transduction in tandem mechanochemical reactions. The mechanochemical activation of [4]-ladderane/ene has been studied and found to exhibit cascade unzipping and a consistent stereochemical distribution of products under various conditions and in different polymer backbones. Ab initio steered molecular dynamics simulations revealed unique non-equilibrium dynamic effects in the mechanochemistry of ladderane, cascade activation and reaction pathway bifurcation.