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

ABSTRACT A terrylene bisimide (TBI) derivative 1 bearing bulky meta ‐terphenyl imide substituents is shown to self‐assemble into helical [1 4 ] 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 Δ G = −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 . 1 4 . 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 toward 1:2 complexes [C . 1 . C] where each TBI is surrounded by two coronene neighbors. Single crystal X‐ray analyses of the pristine [1 4 ] tetramer stack as well as the [P . 1 4 . P] hexalayer stack and the 1:2 trilayer [C . 1 . C] unambiguously confirm the unique stacking arrangements.