Self‐Assembled Bent Perylenediimides

The properties of π-functional materials are predominantly influenced by both their molecular structures and interactions between π-systems. Recent advancements have focused on modifying the geometry or topology of π-molecules from planar to nonplanar conformations to tailor molecular properties. However, the interactions among nonplanar π-molecules remain largely unexplored, likely due to the significant reduction in contact surfaces arising from their curved structures. Herein, we investigated the electro-optical properties and π-stacking behaviors of a series of bent perylenediimides (B-PDIs) with gradual changes in bending angles, achieved by altering the lengths of linear alkyl chains connecting the two nitrogen positions of each PDI. Curvature-dependent self-assembly of these bent PDIs is observed, which is primarily driven by dipole-dipole interactions rather than dispersion forces. More importantly, fine-tuning intermolecular coupling through bending enables excited-state symmetry-breaking charge separation in [n]B-PDIs (n = 16, 12) in the crystalline solid state.