Unlocking a (Pseudo)‐Mechanically Interlocked Molecule with a Coronene “Shoehorn”
A mechanically interlocked molecule (MIM) comprising a tetragold metallobox and a tetraoctynyl-pyrene guest that can be regarded as a pseudo-metallosuitane is described. In contrast to other MIMs, the tetrasubstituted guest can be released from this molecule by the addition of coronene through a “shoehorning” mechanism.
Mechanically interlocked molecules (MIMs) have gained increasing interest during the last decades, not only because of their aesthetic appeal, but also because their unique properties have allowed them to find applications in nanotechnology, catalysis, chemosensing and biomedicine. Herein we describe how a pyrene molecule with four octynyl substituents can be easily encapsulated within the cavity of a tetragold(I) rectangle-like metallobox, by template formation of the metallo-assembly in the presence of the guest. The resulting assembly behaves as a mechanically interlocked molecule (MIM), in which the four long limbs of the guest protrude from the entrances of the metallobox, thus locking the guest inside the cavity of the metallobox. The new assembly resembles a metallo-suitane, given the number of protruding long limbs and the presence of the metal atoms in the host molecule. However, unlike normal MIMs, this molecule can release the tetra-substituted pyrene guest by the addition of coronene, which can smoothly replace the guest in the cavity of the metallobox. Combined experimental and computational studies allowed the role of the coronene molecule in facilitating the release of the tetrasubstituted pyrene guest to be explained, through a process that we named “shoehorning”, as the coronene compresses the flexible limbs of the guest so that it can reduce its size to slide in and out the metallobox.
Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Susana Ibáñez, Katarzyna Świderek, Eduardo Peris