Three-Dimensional Pyrene-Fused N-Heteroacenes

[Image: see text] Four three-dimensional (3D) pyrene-fused N-heteroacenes (P1–P4) are designed and synthesized. From P1 to P4, their lengths are extended in an iterative way, where the thiadiazole unit can be reduced to diamine and the obtained diamines can be further condensed with the diketones with a thiadiazole unit. Compared to their two-dimensional counterparts, the solubility of these 3D pyrene-fused N-heteroacenes is improved by this 3D covalent linkage with two-dimensional units. The diameters of P1–P4 are 3.66, 6.06, 8.48 and 10.88 nm, respectively, and these 3D molecules are characterized by (1)H, (13)C and 2D NMR, MS, UV–vis, PL and CV spectra. Our strategy shows a promising way to large 3D pyrene-fused N-heteroacenes.