"Lock and Key" and "Induced-Fit" Host-Guest Models in Two Digold(I)-Based Metallotweezers.

Two different metallotweezers, each with two pyrene-imidazolylidene-gold(I) arms, were used as hosts for a series of planar aromatic guests. The metallotweezer with a dibenzoacridinebis(alkynyl) spacer ( 1 ) orients the two pyrene-imidazolylidene-gold(I) arms in a parallel disposition, with an interpanel distance of about 7 Å. The second metallotweezer ( 2 ) contains a carbazolylbis(alkynyl) spacer that directs the two pyrene panels in a diverging orientation. Determination of the association constants via 1 H NMR titrations demonstrates that the binding strength shown by 1 is significantly larger than that found by 2 , with binding affinities as large as 10 4 M -1 (in CDCl 3 ), for the encapsulation of N , N '-dimethylnaphthalenetetracarboxydiimide with 1 . The differences in the binding affinities are due to binding models associated with formation of the related host-guest complexes. While 1 operates via a "lock and key" model, in which the host does not suffer distortions upon formation of the inclusion complex, 2 operates via a guest-induced fit model. The large association constants shown by 1 with two planar guests were used for promotion of the template-directed synthesis of 1 , which in the absence of an external template is produced in an equimolecular mixture with its self-aggregated congener, clippane [ 1 2 ]. This observation strongly suggests that the mechanically interlocked clippane is formed through a self-template-directed mechanism, while bonds are broken/formed during the synthetic protocol.