Azulene is a non‐benzenoid aromatic building block with unique chemical structure and physicochemical properties. By using the “bottom‐up” synthetic strategy, we synthesized three azulene‐embedded [n]helicenes ([n]AzHs, n=5, 6 and 7), in which one terminal azulene subunit was fused with n‐2 benzene rings. P‐ and M‐enantiomers were observed in the packing diagrams of [5]‐, and [6]AzHs. However, P‐ and M‐[7]AzHs could be isolated by recrystallization of the racemic mixture. These [n]AzHs were endowed with new properties through the azulene moiety such as low‐lying first electric state (S1), small optical energy gap and anti‐Kasha emission. [6]‐, and [7]AzHs exhibit strong chiroptical responses with high absorption dissymmetry factor (gabs) maxima of about 0.02, which is among the highest |gabs| values of helicenes in the visible range. These azulene‐embedded [n]helicenes contribute to the non‐benzenoid helicene library and allow the structure–property relationships to be better understood.

Two poly(2,6-azuleneethynylene)s (PAzE-1 and PAzE-2) were designed and synthesized. The 2,6-azulene units are head-to-tail-arranged in PAzE-1, while there are three types of orientations of 2,6-azulene units in PAzE-2: head-to-tail, head-tohead, and tail-to-tail segments, of which the head-to-tail one accounts for about 27% (determined from 1 H NMR spectra). Such a structural distinction endows the two polymers with different absorption spectra in solution and aggregation states as well as different thin-film morphologies, microstructures, and field-effect transistor (FET) performances, suggesting that the dipole orientation of azulene units in a polymer backbone may be a critical issue that deserves careful consideration during the molecular design and synthesis. PAzE-1 with an ordered dipole orientation has stronger aggregation even in a very dilute solution (10 −6 M). PAzE-2 films have a higher in-plane microstructural order and lower surface roughness than PAzE-1 films; hence, the PAzE-2-based transistor devices exhibit 1−2 orders higher hole and electron mobilities. Unlike typical p-type alkyl-substituted poly(pphenyleneethynylene)s (PPEs), PAzE-1 and PAzE-2 are ambipolar semiconductors.

A series of scarce tetrahydropyridinofullerenes were synthesized by the metal-free-mediated reaction of [60]fullerene with cheap and easily available α-methyl-substituted arylmethanamines and aldehydes in the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and 4-dimethylaminopyridine (DMAP) in moderate to good yields comparable to the previously reported data for most monoadducts. The in situ generation of azadienes played a crucial role in the successful synthesis of tetrahydropyridinofullerenes. A plausible reaction mechanism was proposed to elucidate the reaction process.