Effect of Charge State on the Equilibrium and Kinetic Properties of Mechanically Interlocked [5]Rotaxane: A Molecular Dynamics Study

[Image: see text] Rotaxanes can exhibit stimuli-responsive behavior by allowing positional fluctuations of their rota groups in response to physiochemical conditions such as the changes in solution pH. However, ionic strength of the solution also affects the molecular conformation by altering the charge state of the entire molecule, coupling the stimuli-responsiveness of rotaxanes with their conformation. A molecular-scale investigation on a model system can allow the decoupling and identification of various effects and can greatly benefit applications of such molecular switches. By using atomistic molecular dynamics simulations, we study equilibrium and kinetics properties of various charge states of the [5]rotaxane, which is a supramolecular moiety with four rotaxanes bonded to a porphyrin core. We model various physiochemical charge states, each of which can be realized at various solution pH levels as well as several exotic charge distributions. By analyzing molecular configurations, hydrogen bonding, and energetics of single molecules in salt-free water and its polyrotaxanated network at the interface of water and chloroform, we demonstrate that charge-neutral and negatively charged molecules often tend to collapse in a way that they can expose their porphyrin core. Contrarily, positively charged moieties tend to take more extended molecular configurations blocking the core. Further, sudden changes in the charge states emulating the pH alterations in solution conditions lead to rapid, sub-10 ns level, changes in the molecular conformation of [5]rotaxane via shuttling motion of CB6 rings along axles. Finally, simulations of 2D [5]rotaxane network structures support our previous findings on a few nanometer-thick film formation at oil–water interfaces. Overall, our results suggest that rotaxane-based structures can exhibit a rich spectrum of molecular configurations and kinetics depending on the ionic strength of the solution.