A Terrylene Bisimide based Universal Host for Aromatic Guests to Derive Contact Surface-Dependent Dispersion Energies

<p>Additional data to report <a href="https://doi.org/10.1002/anie.202318451">https://doi.org/10.1002/anie.202318451</a>:<br><br>&pi;&ndash;&pi; interactions are among the most important intermolecular interactions in supramolecular systems. Here we determine experimentally a universal parameter for their strength that is simply based on the size of the interacting contact surfaces. Toward this goal we designed a new cyclophane based on terrylene bisimide (TBI) &pi;-walls connected by&nbsp;<em>para</em>-xylylene spacer units. With its extended &pi;-surface this cyclophane proved to be an excellent and universal host for the complexation of &pi;-conjugated guests, including small and large polycyclic aromatic hydrocarbons (PAHs) as well as dye molecules. The observed binding constants range up to 10⁸ M^&minus;1&nbsp;and show a linear dependence on the 2D area size of the guest molecules. This correlation can be used for the prediction of binding constants and for the design of new host&ndash;guest systems based on the herewith derived universal Gibbs interaction energy parameter of 0.31 kJ/mol&Aring;² in chloroform.</p>