Dimensional matching vs. induced‐fit distortions. Binding affinities of planar and curved polyaromatic hydrocarbons with a tetra‐gold metallorectangle

A tetragold(I) rectangle-like metallocage containing two pyrene-bis-imidazolylidene ligands and two carbazolyl-bis-alkynyl linkers is used for the encapsulation of a series of polycyclic aromatic hydrocarbons (PAHs), including corannulene. The binding affinities obtained for the encapsulation of the planar PAHs guests in CD2 Cl2 are found to exponentially increase with the number of pi-electrons of the guest (1.3 > logK >6.6). For the bowl-shaped molecule of corannulene, the association constant is much lower than the expected one according to its number of electrons. The molecular structure of the host-guest complex formed with corannulene shows that the molecule of the guest is compressed, while the host is expanded, thus showing an interesting case of artificial mutual induced-fit arrangement.