Self-Assembly of Aligned Hybrid One-Dimensional Stacks from Two Complementary π-Bowls

Designed synthesis of a new crystalline donor–acceptor organic hybrid has been accomplished by using two bowl-shaped polycyclic aromatic hydrocarbons (PAHs) having complementary structures and properties, namely, C 20 H 10 and C 5 -C 20 H 5 (CF 3 ) 5 . The X-ray structural characterization of the product, [(C 20 H 10 )·(C 20 H 5 (CF 3 ) 5 )]·C 6 H 4 Cl 2, revealed the formation of aligned columnar stacks of alternating C 20 H 10 and C 20 H 5 (CF 3 ) 5 molecules with centroid-to-centroid distances of 3.658(8) and 3.787(8) Å and a small bowl slip of 0.086(6) Å. The tight bowl packing is accompanied by notable molecular geometry adjustments of the individual PAHs. The bowl depth increased for corannulene (Δ = +0.019 Å) and decreased for sym -pentakis(trifluoromethyl)corannulene (Δ = −0.011 Å), facilitating enhancement of concave–convex interactions along the stacks. The parallel alignment of one-dimensional columns is supported by multiple intermolecular interactions involving C 6 H 4 Cl 2 used as the crystallization solvent, forming an infinite two-dimensional network in the solid state.