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, C20H10 and C-5-C20H5(CF3)(5). The X-ray structural characterization of the product, [(C20H10)center dot(C20H5(CF3)(5))]center dot C6H4C12, revealed the formation of aligned columnar stacks of alternating C20H10 and C20H5(CF3)(5) molecules with centroid-to-centroid distances of 3.658(8) and 3.787(8) angstrom and a small bowl slip of 0.086(6) angstrom. The tight bowl packing is accompanied by notable molecular geometry adjustments of the individual PAHs. The bowl depth increased for corannulene (Delta = +0.019 angstrom) and decreased for sym-pentakis(trifluoromethyl)corannulene (Delta = -0.011 angstrom), facilitating enhancement of concave convex interactions along the stacks. The parallel alignment of one-dimensional columns is supported by multiple intermolecular interactions involving C6H4C12 used as the crystallization solvent, forming an infinite two-dimensional network in the solid state.