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

• Published in: Angewandte Chemie International Edition Vol. 61; no. 18; pp. e202201494 - n/a
• Main Authors: Duan, Chao, Zhang, Jianwei, Xiang, Junjun, Yang, Xiaodi, Gao, Xike
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 25-04-2022
• Edition: International ed. in English
• Subjects: Azulene; Benzene; Enantiomers; Energy gap; Helicenes; Non-Benzenoid Aromatics; Physicochemical properties; Polycyclic Aromatic Hydrocarbons; Recrystallization; Azulene; Helicenes; Polycyclic Aromatic Hydrocarbons; Non-Benzenoid Aromatics
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202201494

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.
A straightforward “bottom‐up” approach has been used to synthesize azulene‐embedded pristine [n]helicenes (n=5, 6 and 7) that show low‐lying first electric states, small optical energy gaps, and anti‐Kasha emissions. These azulene‐embedded [n]helicenes contribute to the non‐benzenoid helicene library and allow structure–property relationships to be better understood.