Self-assembled Helical Tetramer Stack of Terrylene Bisimide in Solution and Crystalline State

Additional data to report: https://doi.org/10.1002/anie.2434302 A terrylene bisimide (TBI) derivative 1 bearing bulky meta-terphenyl imide substituents is shown to self-assemble into helical [14] tetramer stacks in solution. Driven by strong dispersion and electrostatic forces, a direct transition from monomers into defined tetramers is already observed in the micromolar concentration range (~10-6 M) in methylcyclohexane at room temperature, corresponding to a π–π-interaction strength of DG = -40.1 kJ mol-1 for the respective π–π-stacking interaction between two neighboring TBIs. Upon addition of perylene (P), a further growth of the stacks toward [P.14.P] hexalayers is observed where the guest molecules are stacked at the peripheral positions. In contrast, upon addition of the larger coronene (C), the equilibrium shifts towards 1:2 complexes [C.1.C] where each TBI is surrounded by two coronene neighbors. Single crystal X-ray analyses of the pristine [14] tetramer stack as well as the [P.14.P] hexalayer stack and the 1:2 trilayer [C.1.C] unambiguously confirm the unique stacking arrangements.