Programming permanent and transient molecular protection via mechanical stoppering† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c9sc03744f

A macrocycle (permanently or transiently) protects a viologen from heterogenous reduction, all thanks to bespoke mechanical stoppering.
Chemical protection is an essential tool in synthetic chemistry, which involves blocking reactive sites on a molecule through covalent bonds. Physical approaches, such as encapsulation and host-mediated protection, have emerged as interesting alternatives that use steric bulk to inhibit reactivity. Here, we report the protection of a redox-active viologen through its incorporation into mechanically interlocked molecules (MIMs), namely hetero[4]rotaxanes. The viologen was confined inside a host cavity and flanked by two mechanical stoppers, which allowed for permanent and transient protection. Deprotection occurred on-demand via an unstoppering process, triggered by a proton transfer, polarity effect, or a thermal stimulus. We anticipate that permanent and transient mechanical stoppering could be incorporated into devices to function as molecular probes, transport/delivery systems, or stimuli-controlled degradable materials.