1. Where Ion Mobility and Molecular Dynamics Meet To Unravel the (Un)Folding Mechanisms of an Oligorotaxane Molecular Switch
- Author
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Edwin De Pauw, Emeline Hanozin, Damien Sluysmans, Benoît Mignolet, Anne-Sophie Duwez, Denis Morsa, Françoise Remacle, and J. Fraser Stoddart
- Subjects
Molecular switch ,chemistry.chemical_classification ,010405 organic chemistry ,General Engineering ,General Physics and Astronomy ,Context (language use) ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Folding (chemistry) ,Molecular dynamics ,chemistry ,Computational chemistry ,Chemical physics ,Intramolecular force ,Molecule ,General Materials Science ,Counterion ,Protein secondary structure - Abstract
At the interface between foldamers and mechanically interlocked molecules, oligorotaxanes exhibit a spring-like folded secondary structure with remarkable mechanical and physicochemical properties. Among these properties, the ability of oligorotaxanes to act as molecular switches through controlled modulations of their spatial extension over (un)folding dynamics is of particular interest. The present study aims to assess and further characterize this remarkable feature in the gas phase using mass spectrometry tools. In this context, we focused on the [4]5NPR+12 oligorotaxane molecule complexed with PF6– counterion and probed its co-conformational states as a function of the in-source-generated charge states. Data were interpreted in light of electronic secondary structure computations at the PM6 and DFT levels. Our results highlight two major co-conformational groups associated either with folded compact structures, notably stabilized by intramolecular π–π interactions and predominant for low charge state...
- Published
- 2017