Azulene‐Embedded [n]Helicenes (n=5, 6 and 7)

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.