Ternary π-π Stacking Complexes by Allosteric Regulation in Multilayer Nanographenes.

Construction of π-π stacking supramolecular complexes with more than two different components is challenging due to the weak and directionless nature of dispersion interactions. Here, we report ternary complexes of a ditopic nanographene tetraimide (), α-substituted phthalocyanine (), and polyaromatic hydrocarbons (PAHs) in solution and the crystalline state via allosteric regulation. Binding of one gives rise to significant distortion and conformational changes in that in turn lead to the inhibition of the second binding of . The conformational changes associated with first binding allowed an allosteric binding of a third component (PAHs) to form ternary complexes in solution. H NMR titration revealed moderately high thermodynamic stability for the ternary complexes in CDCl. Competition between allosterically regulated ternary complexes ([··PAH]) and 1:2 stoichiometric binary complexes of with PAHs ([PAH··PAH]) was elucidated. Further, the selective formation of ternary complexes in solution led to the generation of ternary cocrystals from a 1:1:1 mixture of three components in solution. Our work shows that large π-conjugated nanographenes designed with allosteric recognition sites allow the construction of multilayer ternary complexes in solution and the solid state even with dispersive π-π interactions.